Curable composition and its use

ABSTRACT

The curable composition of the present invention contains (A1) a silyl-containing ethylene/α-olefin/non-conjugated polyene random copolymer rubber which has a structural unit derived from a norbornene compound as the non-conjugated polyene with at least one specific vinyl group at the terminal and contains a specific hydrolyzable silyl group, and (B) a compound, other than the rubber (A1), having a hydroxyl group and/or a hydrolyzable group, e.g., (B1) a compound having a silanol group and/or a compound which can react with moisture to form a compound having a silanol group in the molecule. 
     This compound improves elongation of the cured product and residual surface tackiness, and, at the same time, is high in curing speed and capable of giving the cured product of high resistance to weather. It is suitable for, e.g., adhesives, tackifiers, paints, sealants, waterproof materials, spray materials, shaping materials and casting rubber materials.

FIELD OF THE INVENTION

The present invention relates to a curable composition containing asilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber which has a structural unit derived from a norbornenecompound as the non-conjugated polyene with a specific terminal vinylgroup, and contains a specific hydrolyzable silyl group in the molecule,and also to use of the same.

BACKGROUND OF THE INVENTION

(1) A number of methods have been proposed for producing a propyleneoxide-based polymer having at least one reactive, functional silicongroup in the molecule, as described later, and some of them are alreadyproduced industrially. An organic polymer with polyoxy propylene formingas the main chain and functional methoxy silyl group bound to theterminal, e.g., the one produced and sold by Kaneka Corporation (MSPolymer™), may be insufficient in elongation of the cured product andhave residual tackiness on the surface, depending on its purposes, dueto the effects of the composition and service conditions.

Japanese Patent Laid-Open Publication No.34066/1986 discloses acomposition of improved tensile characteristics, characterized in thatit comprises a propylene oxide-based polymer having at least onereactive, functional silicon group in the molecule, a compound havingone silanol group in the molecule, and/or a compound which can reactwith water to form a compound having one silanol group in the molecule.Japanese Patent Laid-Open Publication No.34067/1986 discloses a curable,elastic composition, characterized in that it comprises an organicvinyl-based polymer having at least one reactive, functional silicongroup in the molecule, a compound having one silanol group in themolecule, and/or a compound which can react with water to form acompound having one silanol group in the molecule.

Therefore, there are demands for a curable elastic composition (curablerubber composition) improved in elongation of the cured product and inresidual tackiness, and, at the same time, high in curing speed andcapable of giving the cured product of high resistance to weather.

(2) It is known that a saturated hydrocarbon-based polymer (which isessentially free of an unsaturated C—C bond, except aromatic ring)having at least one reactive silicon group in the molecule showsinteresting nature that it is crosslinked even at room temperature bythe hydrolysis of the reactive silicon group with moisture or the like,followed by formation of the siloxane bond to form a rubber-like curedproduct, wherein the “reactive silicon group” means thesilicon-containing group which has a hydrolyzable group bound to thesilicon atom and can form the siloxane bond.

Such a saturated hydrocarbon-based polymer has the main chain composedof a saturated hydrocarbon, which is resistant to heat-or light-causeddeterioration, can give a cured product excellent in resistance to heatand weather, and gas-barrier property. The saturated hydrocarbon-basedpolymer, therefore, can find uses, e.g., sealant for laminated glass andelastic sealant for buildings.

A silanol condensing catalyst can be used for crosslinking/curing apolymer having a reactive silicon group. Use of this type of catalystcan reduce curing time. In particular, a sealant for laminated glass, aproduct which must be delivered in a very short procurement period, isrequired to be cured very quickly. As such, a strong, silanol-condensingcatalyst is required for the above purposes.

Japanese Patent Laid-Open Publication No. 41360/1996 discloses a curablecomposition which uses a compound represented by the general formulaQ₂Sn(OZ)₂ or [Q₂Sn(OZ)]₂O (wherein, Q is a monovalent hydrocarbon groupof 1 to 20 carbon atoms; and Z is an organic group having a functionalgroup which can form a coordinate bond with Sn within its structure or amonovalent hydrocarbon group of 1 to 20 carbon atoms) serving as thesilanol condensing catalyst to accelerate curing of a saturatedhydrocarbon-based polymer having a reactive silicon group. These curingcatalysts tend to accelerate curing of the saturated hydrocarbon-basedpolymer faster than a divalent tin-based curing catalyst (e.g., tinoctylate) or tin carboxylate catalyst (e.g., dibutyl tin dilaurate).However, curing time is required to be still shorter for a sealant forlaminated glass, a product which must be delivered in a very shortprocurement period.

Several additives have been proposed to accelerate the silanolcondensation for a saturated hydrocarbon-based polymer having a reactivesilicon group. For example, Japanese Patent Laid-Open Publication No.97562/1990 discloses a curable composition which uses “apolyhydroxymonosilane having two or more silicon-bonded hydroxyl groupsin the molecule.” Japanese Patent Laid-Open Publication No. 196842/1990discloses a curable composition which uses “a silicon compound, otherthan polysiloxane, having two or more silicon-bonded hydroxyl groups andtwo or more silicon atoms in the molecule.” Incorporation of one ofthese silanol compounds does improve curability, which, however, isstill insufficient, and a more effective additive is in demand.

A sealant for laminated glass is required to have non-primer adhesion,i.e., to be fast adhesive to a variety of objects in the absence of aprimer. More recently, the above property has been required not only forsealant for laminated glass but also for sealant for other purposes,e.g., by elastic sealant for buildings, to improve applicationefficiency by dispensing with a primer. However, the sealant which usesthe above-described saturated hydrocarbon-based polymer containing areactive silicon group is insufficient in adhesion in the absence of aprimer.

Japanese Patent Laid-Open Publication No. 116832/1999 describes that theinventors have found, after having extensively studied to solve theabove problems, that the composition can have improved curing speed andadhesion without causing any problem, e.g., deteriorated properties ofthe cured product, when incorporated with a specific compound, reachingthe invention.

The invention disclosed by the above publication relates to a curablecomposition of improved curing speed and adhesion, characterized in thatit comprises (A) a saturated hydrocarbon-based polymer having at leastone reactive silicon group, (B) a tetravalent tin compound, and (C) asilicon compound represented by the general formula R¹ _(a)Si(OR²)_(4-a)(wherein, R¹ and R² are each a hydrocarbon group of 1 to 20 carbonatoms, which may be substituted or not substituted; and “a” is aninteger of 0 to 3), in particular, comprising (A) 100 parts by weight ofa saturated hydrocarbon-based polymer having at least one reactivesilicon group in the molecule and molecular weight of 500 to 50,000, (B)0.1 to 20 parts by weight of a tetravalent tin alcoholate, and/or (C)0.01 to 20 parts by weight of a silicon compound represented by thegeneral formula R¹ _(a)Si(OR²)_(4-a) (wherein, R¹ is an aryl group of 1to 20 carbon atoms; R² is a hydrocarbon group of 1 to 20 carbon atoms,which may be substituted or not substituted; and “a” is an integer of 0to 3).

The inventors of the present invention have double-checked the curablecomposition described in the above publication, to confirm that itscuring speed is admittedly improved but still insufficient.

Therefore, there are demands for a curable rubber composition stillhigher in curing speed, and more excellent in adhesion to a variety ofobjects and resistance to weather.

(3) One example of the reactive silicon group is represented by theformula —Si(OCH₃)₃ and hydrolyzable with moisture in air into —Si(OH)₃,which reacts with another reactive silicon group through silanolcondensation to form a siloxane bond (Si—O—Si). Therefore, the polymercontaining a reactive silicon compound can be crosslinked/cured in thepresence of moisture even at room temperature. Of these polymers, anoxyalkylene polymer with, e.g., polyoxypropylene in the main chainskeleton, has been widely used as sealant for buildings and otherindustrial purposes, because of its characteristics, e.g., liquid atroom temperature and curable into a rubber elastomer. However, when itis used to fill a joint (i.e., gap between the construction material,e.g., wall material) or the like, it leaves residual tackiness on thecured product surface, even after it is cured, deteriorating the outerappearances resulting from contamination of the surface with dust or thelike. A paint may be applied to the cured product surface. In this case,the paint is not always sufficiently adhesive to the sealant surface, inparticular when a solvent-based paint is used.

Japanese Patent Laid-Open Publication No. 302213/1997 discloses acurable composition comprising (a) an oxyalkylene polymer containing atleast one reactive silicon group in the molecule, and (b) a siliconcompound containing at least one amino group and at least one trialkylsiloxy group in the molecule. It is claimed to leave residual tackinessto only a limited extent, after it is cured, and to be highly adhesiveto a paint.

Nevertheless, improvements of these characteristics are stillinsufficient, and more improvements in curing speed and resistance ofthe cured product to weather are demanded.

Therefore, there are demands for a curable composition high in curingspeed, leaving little residual tackiness on the cured product surface,after it is cured, highly resistant to weather, showing high adhesionbetween a paint and sealant surface, when the former is applied, anduseful for sealant, primer or the like.

(4) RTV (room temperature vulcanizable) silicone rubber is well known asa polymer curable even at low temperature (room temperature) to form arubber-like material, and has been used for sealants for buildings and avariety of formed materials. However, RTV silicone rubber, havingpolysiloxane in the main chain, is expensive and insufficient in someproperties.

Therefore, a rubber-based organic polymer curable at room temperaturelike RTV silicone rubber is proposed by, e.g., Japanese Patent Laid-OpenPublication No. 156599/1975. It has a rubber-based organic polymerinstead of polysiloxane in the main chain.

The polymer has a functional, reactive silicon group which is curable byforming the siloxane bond and is curable even at room temperature, likeRTV silicone rubber, to form a rubber-like material by the followingreaction. It is cheaper than polysiloxane, and has characteristics whichpolysiloxane lacks.

wherein, X′ is a hydrolyzable group.

Rubber is generally required to have tensile characteristics of lowmodulus and high elongation, and so is a rubber-based organic polymerhaving the reactive silicon group.

Japanese Patent Laid-Open Publication Nos. 34066/1986 and 34067/1986propose incorporation of monovalent silanol compound or derivativethereof as the method to improve modulus and elongation of a curedrubber-based organic polymer having a reactive silicon group.

The compound disclosed by each of the above publications may not alwaysimprove modulus and elongation sufficiently, and may leave problems,even when modulus and elongation are improved, e.g., insufficient curingof the cured product to leave tackiness on the surface, insufficientproperties for formed materials or sealants, and poor storage stabilityof the composition. In other words, few conventional curablecompositions containing a rubber-based organic polymer having a reactivesilicon group satisfy all of the requirements of excellent modulus andelongation of the cured product, free of residual tackiness on the curedproduct surface, and excellent storage stability of the composition.

Japanese Patent Publication No. 96648/1995 discloses a combination ofrubber-based organic polymer and organosiloxane compound, the formerhaving a functional, reactive silicon group crosslinking-cured by thesiloxane bond. However, it is still insufficient in curing speed andresistance to weather, among others.

Therefore, there are demands for a curable composition containing arubber-based organic polymer having a reactive, functional silicongroup, which is rapidly cured with moisture, excellent intensile-related properties, capable of giving a rubber-like elastomerfree of residual tackiness on the surface, and improved in resistance toweather and storage stability.

(5) It is already known that a vinyl-based resin containing ahydrolyzable silyl group is hydrolyzed at normal temperature withmoisture in air to form a resin of dense network structures, excellentin, e.g., gloss, resistance to weather, discoloration and solvent,hardness, and adhesion to inorganic base materials.

A vinyl-based resin containing a hydrolyzable silyl group can find wideuses, e.g., paint, adhesive, coating material, sealant and binder,because of its favorable characteristics described above.

However, a vinyl-based resin containing a hydrolyzable silyl group isnot always satisfactory in adhesion to organic base materials. Forexample, a paint for repairing automobiles is required to be adhesive tocoating films of various conventional paints, in particular to melamineacrylic and melamine alkyd paints.

One of the known methods to improve adhesion to melamine acrylic andmelamine alkyd paints is incorporation of an amine-based silane couplingagent or modification thereof, which, however, may cause problems, e.g.,reduced storage stability of the vinyl-based copolymer containing ahydrolyzable silyl group and its tendency to coloration.

Japanese Patent Laid-Open Publication No. 75567/1989 discloses a resincomposition curable at room temperature, comprising (A) 100 parts byweight of a vinyl-based polymer containing a silyl group, with the mainchain essentially composed of a vinyl-based polymer chain and at leastone silicon atom bonded to a hydrolyzable group at the terminal or inthe side chain in the molecule, (B) 0.1 to 100 parts by weight of aspecific silane compound, and (C) 0 to 20 parts by weight of a curingcatalyst. It describes that vinyl-based copolymer containing ahydrolyzable Silyl group can have greatly improved adhesion to melaminealkyd paint or melamine acrylic paint, when incorporated with a specificsilane compound, and that the resin composition curable at roomtemperature is found to have improved properties, e.g., hardness, andresistance to solvent and contamination of the cured coating film.

However, the composition is not always satisfactory in resistance toweather. The publication is completely silent onethylene/α-olefin/non-conjugated polyene random copolymer rubber.

Therefore, there are demands for a rubber composition curable at roomtemperature, high in curing speed, excellent in resistance to weather,and capable of giving its highly adhesive cured product.

(6) A compound having a reactive silyl group is used for variouspurposes, e.g., paint, coating material, silane coupling agent, adhesivefor rubber and sealant, for reactivity of its silyl group. Inparticular, the compound having a condensed silyl group curable at roomtemperature, having a reactive group, e.g., hydroxy, acetoxy, oxime oralkoxy group, has found wide applications.

The compound having a condensed silyl group curable at room temperatureis hydrolyzed normally in the presence of a curing catalyst, althoughthe hydrolysis proceeds with moisture in air in the absence of thecatalyst. The well-known curing catalysts include organotin compounds,e.g., dibutyl tin dilaurate and dibutyl tin dimaleate. However, they areslow in curing speed, showing little curing acceleration effect underheating at low temperature of around 60 to 80° C., and still low curingspeed even at baking temperature of 120 to 300° C. Therefore, there aredemands for a catalyst higher in curing speed than the conventionalorganotin compound. There are problems to be solved when the catalyst isused for repairing automobiles and coating bridges, which need aquick-drying paint, and for the purposes which need a simple coatingsystem, e.g., production lines for new vehicles, curtain walls andprecoated metals.

Japanese Patent Laid-Open Publication No. 660/1990 discloses a curablecomposition containing, as the effective ingredients;

-   (A) at least one type of compound containing a silyl group selected    from the group consisting of polyester having at least one type of    specific silyl group, vinyl-based copolymer with acrylic or    methacrylic acid, diallyl phthalate-based compound and diallyl    phthalate-based copolymer,-   (B) an amine compound selected from the group consisting of    aliphatic amine, alicyclic amine, modified cycloaliphatic polyamine    and ethanol amine,-   (C) a silane coupling agent, represented by the general formula    Y₃—Si-Z, wherein Y is an alkoxyl group; and Z is an alkyl group    containing a functional group selected from the group consisting of    an amino group which may be substituted with an aminoalkyl group or    mercapto group), and-   (D) a lacquer-based paint, an acryl lacquer-based paint, an acrylic    resin-based paint, a thermosetting acrylic-based paint, an alkyd    paint, a melamine paint, an epoxy-based paint, or    organopolysiloxane.

The publication also describes that a silyl-containing compound having ahydrolyzable group can be cured faster, in particular under heating,when incorporated with a catalyst quantity of a specific amine compoundand silane coupling agent, and further with a lacquer-based, acryllacquer-based, acrylic resin-based, thermosetting acrylic-based paint,alkyd paint, melamine paint, epoxy-based paint, or organopolysiloxane,without causing any adverse effect on properties of the cured product oflacquer-based, acryl lacquer-based, acrylic resin-based, thermosettingacrylic-based paint, alkyd paint, melamine paint, epoxy-based paint, ororganopolysiloxane.

However, the inventors of the present invention have double-checked thecomposition to confirm that it is still insufficient in curing speed andunsatisfactory in resistance to weather. It also describes asilyl-containing compound having a hydrolyzable group, but is completelysilent on ethylene/α-olefin/non-conjugated polyene random copolymerrubber.

Therefore, there are demands for a curable rubber composition, easilycured with moisture in air at room temperature or under heating, and athigh speed, and excellent in resistance to weather of the cured product.

(7) Japanese Patent Laid-Open Publication No. 73998/1977, for example,discloses an oxyalkylene-based polymer having a silicon-containing groupwith hydroxyl and/or a hydrolyzable group bonded to the silicon atom,and crosslinkable by forming the siloxane bond (such asilicon-containing group is here in after referred to as reactivesilicon group). It is typically represented by the following generalformula:X″₃Si

Oxypropylene polymer

SiX″₃wherein, X″ is a hydrolyzable group, e.g., methoxy group.

An oxyalkylene-based polymer having a reactive silicon group is cured atroom temperature after forming the siloxane bond (Si—O—Si) between thepolymer molecules by the action of moisture in air, as is the case witha silicon rubber curable at room temperature, to form a rubber-likecured product. The cured product has been used for, e.g., sealant andadhesive, because of its excellent properties, e.g., elongation,strength and adhesion.

The rubber-like cured product, when to be used for sealant or the like,is required to have various properties of which tensile-relatedcharacteristics and adhesion to an object are more important. Thetensile-related characteristics include modulus, elongation and breakingstrength, and low modulus and high elongation as the characteristics ofrubber are frequently required. Adhesion includes adhesive strength toan object and its resistance to weather, and high adhesive strength andhigh resistance to weather are required. In particular, it is frequentlyused as a sealant for buildings for transparent materials, e.g., glass,and is required to have high resistance of adhesive strength to weather,especially while it is irradiated with sunray.

Japanese Patent Laid-Open Publication No. 34066/1986 proposes acomposition comprising an oxyalkylene-based polymer having a reactivesilicon group and a compound having a silanol group in the moleculeand/or a compound having a hydrolyzable silicon group in its moleculereacting with moisture to form a compound with a silanol group in themolecule (hereinafter referred to as monovalent silanol-based compound),as the one which gives a low-modulus cured product.

Japanese Patent Laid-Open Publication No. 182350/1982 discloses use of acompound having amino group and a silicon atom with a hydrolyzablegroup, e.g., γ-aminopropyltrimethoxysilane (H₂NCH₂CH₂CH₂Si(OCH₃)₃) orγ-aminopropylmethyldimethoxysilane (H₂NCH₂CH₂CH₂Si(CH₃) (OCH₃)₂) bondedto the silicon atom, to improve adhesion of the cured product ofoxyalkylene-based polymer having a reactive silicon group.

However, a composition containing a compound having a silicon atom towhich 3 hydrolyzable groups are bonded, e.g.,γ-aminopropyltrimethoxysilane, has a disadvantage of deteriorated effectof the monovalent silanol-based compound, due to increased modulus ofits cured product. On the other hand, a composition containing acompound having a silicon atom to which 2 hydrolyzable groups arebonded, e.g., γ-aminopropylmethyldimethoxysilane, has a disadvantage ofinsufficient resistance of its adhesive strength to weather, althoughits cured product scarcely has an increased modulus.

Japanese Patent Laid-Open Publication No. 117955/1990 proposes acomposition comprising an oxyalkylene-based polymer having a reactivesilicon group and monovalent silanol-based compound, incorporated with acompound having amino group and a silicon atom to which 2 hydrolyzablegroups are bonded, and a small quantity of a compound having amino groupand a silicon atom to which 3 hydrolyzable groups are bonded, as thecurable composition of improved modulus-related properties, adhesivestrength to an object and resistance of adhesive strength to weather.However, the curable product of the above composition is stillinsufficient in resistance to weather, leaving room for furtherimprovement.

Therefore, there are demands for a curable composition high in curingspeed, giving a weather-resistant cured product, and suitable foradhesive, sealant or the like.

(8) Japanese Patent Laid-Open Publication No. 73998/1977, for example,discloses an oxyalkylene-based polymer having a silicon-containing groupwith hydroxyl and/or a hydrolyzable group bonded to the silicon atom,and crosslinkable by forming the siloxane bond (such asilicon-containing group is hereinafter referred to as reactive silicongroup). It is typically represented by the following general formula:X″₃Si

Oxypropylene polymer

SiX″₃wherein, X″ is a hydrolyzable group, e.g., methoxy group.

An oxyalkylene-based polymer having a reactive silicon group is cured atroom temperature after forming the siloxane bond (Si—O—Si) between thepolymer molecules by the action of moisture in air, as is the case witha silicon rubber curable at room temperature, to form a rubber-likecured product. The cured product has been used for, e.g, sealant andadhesive, because of its excellent properties, e.g., elongation,strength and adhesion.

In general, the polymer is frequently used as a composition incorporatedwith a filler for, e.g., cost reduction. However, incorporation of afiller substantially increases the viscosity of the composition, and useof a plasticizer is technically essential to sufficiently reduce theviscosity to make the composition processable by the common method.

In general, use of a filler or plasticizer causes various problems, ofwhich deteriorated storage stability, especially that leading todecreased curing speed of the stored composition, is more serious.

Therefore, there are demands for a curable composition high in curingspeed and storage stability (especially quickly cured when it is used,even after being stored for extended periods), and giving aweather-resistant cured product.

(9) A vinyl-based resin containing silyl group is characterized in thatit is curable at room temperature with moisture, in particular that inair, which opens up wide applicable areas for the composition. However,its disadvantages of short pot life and insufficient resistance toweather have sometimes limited its applications.

Japanese Patent Publication No. 47747/1988 proposes an inventionrelating to a vinyl-based resin composition. The vinyl-based resin (A)containing silyl group for the composition has at least one silyl grouprepresented by

(wherein, R₁ and R₂ are each hydrogen or monovalent hydrocarbon groupselected from the group consisting of alkyl, aryl and aralkyl group of 1to 10 carbon atoms; X is a halogen or a group selected from the groupconsisting of alkoxy, acyloxy, aminoxy, phenoxy, thioalkoxy and aminogroup, at least one being alkoxyl or phenoxy group; and “a” is aninteger of 0 to 2) in the molecule, and also has a molecular weight of1,000 to 20,000.

The publication describes that the curable composition is stable, andcomprising (A) the above vinyl-based resin, (B) an alcohol and/or alkylorthoformate, and (C) an alkoxysilane compound. It also describes thatthe invention relates to a composition containing a compound whichcontains a silyl group at the terminal or in the side chain. It iscurable at room temperature with moisture, in particular that in air,which is characteristic of a vinyl-based resin containing a silyl group,and, at the same time, is characterized by stability of long pot life.As such, it is very suitable as a resin for solventless or high solidcontent type paint, which has been attracting much attention as thenon-polluting, energy-saving type paint. In particular, the resin of theinvention, the publication describes, has a lower molecular weight thanthe conventional vinyl-based resin, which brings about a great advantagethat it is applicable more easily to a non-polluting or high solidcontent type paint. The vinyl-based resin containing a silyl group forthe composition of the invention can be easily produced by, e.g.,reacting a vinyl-based resin having a C—C double bond with a hydrosilanecompound in the presence of a catalyst of Group VIII transition metal.

However, the inventors of the present invention have double-checked thecurable composition to confirm that it is still insufficient incurability at room temperature and resistance to weather, although itadmittedly has the above-described characteristics.

Therefore, there are demands for a curable rubber composition high instorage stability and curing speed, and giving a highlyweather-resistant cured product.

(10) A silicon-containing group having a hydrolyzable group bonded tothe silicon atom and crosslinkable by forming a siloxane bond (such agroup is hereinafter referred to as reactive silicon group) may berepresented by —Si (OCH₃)₃, which is a well-known functional group.

This functional group is hydrolyzed with moisture, e.g., that in air,into —Si(OH)₃ or the like, which reacts with another reactive silicongroup to form a siloxane bond (Si—O—Si) by silanol condensation.(CH₃O)₃Si˜˜˜˜˜˜˜˜Si(OCH₃)₃→[(HO)₃Si˜˜˜˜˜˜˜˜Si(OH)₃]→(˜˜˜˜SiO)₃Si˜˜˜˜˜˜˜˜Si(OSi˜˜˜˜)₃

Therefore, a polymer having a reactive silicon group can becrosslinked/cured even at room temperature in the presence of moisture.Of these polymers, the one with a rubber-based main chain skeleton hascharacteristics of being highly viscous liquid at room temperature andbeing cured into a rubber elastomer, and is widely used as sealant forbuildings and other industrial purposes. Such sealant is applied to agap (joint) of a construction material, to fill up and keep it water-andair-tight, after it is cured.

Of these rubber-based polymers, a saturated hydrocarbon-based polymer,e.g., polyisobutylene, can yield a cured product excellent in resistanceto weather and heat, and gas-barrier property. High gas-barrier propertymeans high moisture-blocking property, which is a disadvantage for apolymer to be cured with moisture in air, because it needs a fairly longtime, a week or more, to be thoroughly cured inside, although cured soonon the surface. Japanese Patent Laid-Open Publication No. 185565/1990proposes a composition which is dispersed with a hydrate of metallicsalt to be quickly cured at room temperature to deep inside.

The polymer having a reactive silicon group is frequently used afterbeing incorporated with a silanol condensing catalyst (curing catalyst),filler, plasticizer or the like to form the curable composition. Thecurable compositions may fall into two general categories, one-liquidand two-liquid types. The one-liquid type curable composition is aliquid containing all of the above-described additives. It is convenientin that it needs no mixing procedure before use, but must be keptcompletely dehydrated to prevent curing before use. On the other hand,two-liquid type curable composition is less convenient in that it needsthe mixing procedure before use, but not necessarily kept dehydrated ascompletely as the one-liquid type, because the polymer having a reactivesilicon group will not be cured easily in the absence of the silanolcondensing catalyst, even when moisture is present to some extent.

A hydrate of metallic salt, described above, cannot be used as themoisture source for curing the polymer which is used to produce aone-liquid type curable composition, because curing of the polymer willstart as soon as it is mixed with a silanol condensing catalyst and thehydrate.

Titanium and tin compounds are frequently used as silanol condensingcatalysts. Many of them are decomposed in the presence of moisture, andit is considered that the silanol condensing catalysts are decomposed bya hydrate of metallic salt. Therefore, a hydrate of metallic salt, whenused as the moisture source, is added to a curable compositionimmediately before the composition is used (cured), or to the majoringredient of a two-liquid type composition, i.e., that containing thepolymer component.

However, it is inconvenient to add only the hydrate of metallic saltimmediately before the composition is used (cured). Moreover,incorporation of the hydrate of metallic salt in the major ingredientmay cause another problem i.e., increased viscosity of the majoringredient as a result of curing of the polymer having a reactivesilicon group, although to a limited extent.

A sealant is frequently incorporated with a silane coupling agent as thetackifier. However, a silane coupling agent is liable to react withmoisture, and cannot be added as the additive neither to the majoringredient nor hardening agent. For example, a silane coupling agentsuch as γ-isocyanate propyltrimethoxysilane (ONCCH₂CH₂CH₂Si(OCH₃)₃)reacts with a hydrate of metallic salt when added to the majoringredient, and is decomposed by the silanol condensing catalyst whenadded to the hardening agent, with the result that it will no longerwork as the silane coupling agent for, e.g., increasing tackiness.

Japanese Patent Laid-Open Publication No. 182992/1998 discloses acurable composition. The object of the invention is to provide a curablecomposition of a saturated hydrocarbon-based polymer and a hydrate ofmetallic salt as the moisture source, the former having asilicon-containing group, e.g., a hydrolyzable group of silicon to whichmoisture-curable polyisobutylene is bonded, and crosslinkable by formingthe siloxane bond, as the composition showing no increase in viscositywhile it is being stored. Another object of the invention is to providea curable composition which can incorporate a compound, e.g., that, likea silane coupling agent, having a reactive silicon group readilyreactive with moisture. The invention provides a two-liquid ormulti-liquid type curable composition with hydrate of metallic saltincorporated in a hardening agent containing a silanol condensingcatalyst. In short, the invention provides a two-liquid and multi-liquidtype curable compositions composed of at least two types of liquids of(A) a major ingredient of saturated hydrocarbon-based polymer having ahydrolyzable group bonded to silicon, and a silicon-containing groupcrosslinkable by forming the siloxane bond, and (B) a hardening agentcontaining a silanol condensing catalyst and hydrate of metallic salt.

However, there is still room for improvement in the isobutylene-basedpolymer as the saturated hydrocarbon-based polymer of the invention,because of its insufficient curing speed and resistance to weather.

The publication is silent on a multi-liquid type curable rubbercomposition, composed of at least two types of liquids, containing asilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber which has a structural unit derived from a norbornenecompound as the non-conjugated polyene with a specific terminal vinylgroup, and contains a specific hydrolyzable silyl group in the molecule.

Therefore, there are demands for a curable rubber composition whichincorporates a hydrate of metallic salt as the moisture source, showingno increase in its viscosity while being stored, high in curing speedand resistance to weather, and can incorporate a compound having areactive silicon group readily reactive with moisture, e.g., a silanecoupling agent.

(11) Japanese Patent Laid-Open Publication No. 6041/1988 discloses anisobutylene-based polymer having, at the molecular terminal, asilicon-containing group with hydroxyl or a hydrolyzable group bonded tothe silicon atom and crosslinkable by forming the siloxane bond (such agroup is hereinafter referred to as reactive silicon group). It iscurable even at normal temperature with moisture into a rubber-likecured product excellent in properties, e.g., resistance to heat, waterand weather.

However, the cured product necessarily has a long molecular chain tohave good rubber elasticity, which invariably increases its viscosityand makes it difficult to handle. This disadvantage may limit its use,due to difficulty in application. Decreasing the viscosity of thepolymer to avoid the above problems will invariably cause insufficientelongation-related properties of the polymer. The high moisture-barrierproperty of the cured isobutylene-based polymer may deteriorate itscurability, because of insufficient supply of moisture necessary forcuring.

Japanese Patent Laid-Open Publication No. 252670/1989 proposes, in orderto solve the above problems, a curable resin composition comprising asaturated hydrocarbon-based polymer having at least onesilicon-containing group with hydroxyl or a hydrolyzable group bonded tothe silicon atom and crosslinkable by forming the siloxane bond, andalso an organosilicon polymer. The composition, however, cannot alwayssolve the above problems sufficiently, and is insufficient in resistanceto weather and curing speed of the cured product.

Therefore, there are demands for a composition low in viscosity, good inworkability, sufficient in curing speed, excellent in, e.g., resistanceto weather, heat and water, and capable of giving a rubber-like curedproduct high in strength and elongation (low modulus of elasticity).

(12) The main chain skeleton of an ethylene/α-olefin/non-conjugatedpolyene random copolymer rubber is composed of a structural unit derivedfrom ethylene and that from α-olefin, and a small quantity ofcopolymerized non-conjugated polyene-based monomer as the thirdcomponent to introduce the unsaturated C—C bond necessary forcrosslinking. As a result, it is used as a vulcanizable elastomer whichcan give the vulcanized product much higher in resistance to heat andweather than a diene-based elastomer, e.g., natural rubber, polyisopreneor polybutadiene. However, resistance to weather of the vulcanizedproduct is still damaged by the unsaturated C—C bond for vulcanization,although it has a significantly smaller quantity of the unsaturated C—Cbond than a diene-based elastomer.

Viewed from vulcanization speed, it is slow due to insufficient quantityof the unsaturated C—C bond, limiting speed of the production line forvulcanization. This should be one of the causes for a cost increase.

Therefore, there are demands for a rubber composition high invulcanization speed, improved in resistance to weather and excellent inmechanical strength, while keeping the various favorable characteristicsof an ethylene/α-olefin/non-conjugated polyene random copolymer rubber,e.g., excellent resistance to heat and chemicals of the vulcanizedproduct.

(13) A polymer having a hydrolyzable silyl group (a silicon-containinggroup having hydroxyl or a hydrolyzable group bonded to the siliconatom, and capable of forming the siloxane bond) is crosslinked/cured inthe presence of moisture, and hence can be used as a curablecomposition. Of these polymers, the one with polyether serving as themain chain skeleton is generally known as a modified silicone, and hasbeen widely used for sealant or the like.

A mixture of a polymer having a hydrolyzable silyl group and a curableresin which is compatible with the polymer and curable through adifferent curing reaction shows phase separation when cured, and canform cured products of various layered structure. Properties of a curedproduct obtained from the composition composed of a polymer having ahydrolyzable silyl group and epoxy resin compatible therewith greatlydepend on cohesive force of the matrix. A method is proposed forincorporating a silane coupling agent which controls production of suchcured product and for changing its content, as disclosed by JapanesePatent Laid-Open Publication No. 292616/1992.

The above-described curable composition can be controlled for thelayered structure of the cured product. Therefore, the curable resincomposition can be improved in modulus of elasticity and tensile shearstrength, because size of the dispersed epoxy resin particles and matrixstrength can be changed over a wide range. However, the resincomposition is still insufficient in curing speed and resistance toweather.

Therefore, there are demands for a rubber composition high in adhesionand curing speed, and giving various types of cured products of highresistance to weather and other characteristics, e.g., a cured productof greatly varying layered structures, another cured product of lowmodulus of elasticity and high elongation, or still another curedproduct of high modulus of elasticity and tensile shear strengthrealized by decreasing size of the dispersed epoxy resin particles andincreasing epoxy resin content of the matrix.

(14) A rubber-based organic polymer having a hydrolyzable silyl group,although showing an interesting characteristic that it can be cured evenat room temperature into a rubber elastomer, normally has a disadvantageof insufficient strength of the cured product, which limits itsapplicable areas.

Japanese Patent Laid-Open Publication No. 280217/1987 discloses acurable composition composed of a rubber-based organic polymer having ahydrolyzable silyl group and epoxy resin, incorporated with two types ofsilicon compounds, one having both a functional group reactive with anepoxy group and hydrolyzable silicon group in the molecule, and theother having at least two hydroxyl groups bonded to a silicon atom inthe molecule, in order to overcome the disadvantages of the conventionalcured rubber-based organic polymer having a hydrolyzable silyl group.

Incorporation of these silicon compounds into the curable compositionimproves insufficient strength of the rubber-based organic polymerhaving a hydrolyzable silicon group, and gives the cured product of highstrength irrespective of moisture quantity. The composition, however,still has disadvantages of insufficient curing speed and resistance ofthe cured product to weather.

Therefore, there are demands for a curable rubber composition improvedin toughness and strength, giving the cured product of high strengthirrespective of moisture quantity, and, at the same time, high in curingspeed and giving the cured product of high resistance to weather.

(15) A saturated hydrocarbon-based polymer containing a reactive silicongroup is crosslinked by hydrolysis of the reactive silicon group withmoisture proceeding even at room temperature and subsequent formation ofthe siloxane bond, to give a rubber-like cured product. As such, it isused as sealant for laminated glass and elastic sealant for buildings.

The elastic sealant for buildings is generally incorporated with afiller of calcium carbonate, e.g., gelatinized calcium carbonate orlimestone powder. The composition incorporated with gelatinized calciumcarbonate for sealants is high in thixotropy, has less thready, andhence is high in workability. The cured product is suitable for sealantsfor buildings, because of its tensile-related properties of low modulusand high elongation.

Limestone powder, on the other hand, is used as a bulking agent.

A sealant for laminated glass is required to have a sufficiently highmodulus and strength to support the glass, unlike a sealant forbuildings which is required to have a low modulus and high elongation.It is therefore essential for a sealant for laminated glass to havemechanical properties, e.g., strength and hardness, and, at the sametime, good workability. However, a composition containing a saturatedhydrocarbon-based polymer having a reactive silicon group cannotsimultaneously satisfy these properties.

Japanese Patent Laid-Open Publication No. 316804/1998 discloses asaturated hydrocarbon-based polymer having a reactive silicon groupincorporated with calcium carbonate and talc as the curable compositionthat can solve the problem of inclusively satisfying these properties.However, the proposed composition may not always sufficiently satisfyworkability and mechanical properties. Moreover, it is not alwayssatisfactory in curing speed and resistance to weather of the curedproduct.

Therefore, there are demands for a rubber composition well-balancedbetween workability and mechanical properties of the cured product,sufficient in curing speed and resistance to weather of the curedproduct, and suitable as a sealant for laminated glass.

(16) A curable polymer is a liquid or the like moldable before curing,giving a solid, e.g., rubber-like one, of high strength when cured. Thecurable polymer is widely used for adhesives and sealants. The adhesivesand sealants for glass and plastics are required to have an additionalproperty of resistance to light, because the surface for which they areused is irradiated with light, unlike the ones which are used for opaquematerials. They completely lose the function of adhesive or sealant,when deteriorated with light, because the adhesive layer will peel off.Adhesion is specifically referred to as weather-resistant adhesion, whenit is required to have resistance to light as an important property fortransparent materials. An adhesive or sealant for buildings, inparticular, is required to retain the additional property ofweather-resistant adhesion for extended periods. The adhesion layer isvery thin and will lose weather-resistant adhesion, when it is made of amaterial insufficient in resistance to weather to any extent. There arenot many materials which show excellent weather-resistant adhesion.

A saturated hydrocarbon-based polymer having a crosslinkable silicongroup falling into the category of curable polymers is cured, e.g., bythe actions of moisture in air. When cured, it will show favorablecharacteristics, e.g., high resistance to weather and heat, adhesion inthe presence of water, non-polluting nature, and low moisturepermeability. Moreover, it shows good workability and is sprayedsmoothly, because it can be fluid to have an adequate viscosity andstructural viscosity (thixotropy) at room temperature. In addition, thepolymer is not malodorous, giving off little odor while being handled,and particularly suitable for sealants (Japanese Patent Laid-OpenPublication No. 6041/1988). Japanese Patent Laid-Open Publication No.198673/1989 describes that the above polymer can be used as a sealantalso for transparent material, e.g., laminated glass. When used forlaminated glass, it brings about the merits of increasing lineproduction speed and showing its effect by single sealing, instead ofdouble sealing required for the conventional one, because it can bequickly cured under heating. It can be also used for laminated glassdouble-sealed by the common method, needless to say.

It is found, however, when a curable composition containing a saturatedhydrocarbon-based polymer having a crosslinkable silicon group is usedfor some transparent materials, in particular surface-treated glass suchas heat ray reflective type, the cured composition may not always showsufficient weather-resistant adhesion.

Japanese Patent Laid-Open Publication No.286895/1997 proposes a curablecomposition containing a saturated hydrocarbon-based polymer having acrosslinkable silicon group incorporated with a combination of specificlight stabilizer and silane coupling agent, as the one with improvedweather-resistant adhesion for surface-treated glass. However, its curedproduct is still insufficient in resistance to weather, and there isroom for improvement in its curing speed.

Therefore, there are demands for a curable composition high in curingspeed, giving its cured product of high resistance to weather, andsuitable for adhesives and sealants.

(17) A polyalkylene oxide-based polymer, e.g., polypropylene oxide-basedpolymer, having a reactive silicon group at the terminal of the moleculeis already known. It has a characteristic of being cured with moistureeven at room temperature into a rubber-like solid. However, the polymerhas disadvantages of insufficient resistance to heat, water and weather.

Therefore, there are demands for a curable rubber compositioncontaining, as the main ingredient, a silyl-containing rubber containinga specific hydrolyzable silyl group in the molecule, and giving thecured product excellent in resistance to weather and heat.

(18) A saturated hydrocarbon-based polymer having at least one reactivesilicon-containing group, with hydroxyl or a hydrolyzable group bondedto the silicon atom and crosslinkable by forming the siloxane bond, isknown to show interesting nature that it is crosslinked with moisture orthe like even at room temperature by forming the siloxane bondaccompanied with the hydrolysis or the like of the reactive silicongroup, to form a rubber-like cured product. Therefore, it is useful for,e.g., sealants for laminated glass and elastic sealants for buildings.

A sealant for laminated glass is required to have non-primer adhesion,i.e., to be fast adhesive to various objects in the absence of a primer.More recently, the above property has been required not only for sealantfor laminated glass but also for sealant for other purposes, e.g., byelastic sealant for buildings, to improve application efficiency bydispensing with a primer. However, the sealant which uses theabove-described saturated hydrocarbon-based polymer containing areactive silicon group is insufficient in adhesion in the absence of aprimer.

Moreover, a sealant for laminated glass, in particular that for theglass fringe, is required to be excellent especially inweather-resistant adhesion. The above-described saturatedhydrocarbon-based polymer containing a reactive silicon group is somehowinsufficient in weather-resistant adhesion. In particular, it has adisadvantage of insufficient weather-resistant adhesion for highlyinsulating, heat ray reflective glass, which has been widely usedrecently.

Japanese Patent Laid-Open Publication No.152584/1998 discloses a curablecomposition comprising (A) a saturated hydrocarbon-based polymercontaining at least one reactive silicon group, (B) a silane couplingagent, and (C) a compound containing an unsaturated group in themolecule which triggers polymerization by reacting with oxygen in air,and/or photopolymerizable compound. However, this curable compositionhas still room for improvement both in curing speed and resistance toweather.

Therefore, there are demands for a curable composition containing, asthe main ingredient, a saturated hydrocarbon-based polymer having areactive silicon group which is highly adhesive to various materials,improved in weather-resistant adhesion for various types of glass, inparticular heat ray reflective glass, and excellent in resistance toweather and curing speed.

(19) A silicone-based tack agent of silicone resin based on dimethylpolysiloxane rubber is known as a heat-resistant tack agent.

However, it is generally known that this silicone-based tack agent hasdisadvantages, e.g., strong tackiness with non-polar compounds, e.g.,polytetrafluoroethylene, and compatibility with the so-called siliconereleasing paper coated with a silicone releasing agent, because bothcontain polysiloxane, making itself difficult to peel off the releasingpaper and damaging its releasing effect.

On the other hand, tack agents of good releasing property include thosecomposed of a component having only an organic skeleton, e.g.,rubber-based tack agents, such as natural or synthetic rubberincorporated with a tackifier resin, and acrylic-based tack agentsproduced by copolymerization with an acrylate ester. They have their owndisadvantages; for example, the former is of non-crosslinking type andcannot be expected to have high resistance to heat, while the latter,although crosslinkable by the actions of a crosslinking agent, e.g.,that of isocyanate, incorporated therein, may not give the crosslinkedproduct itself showing sufficient resistance to heat. Therefore, theymay not show sufficient resistance to heat as a tack agent.

Recently, use of a group containing hydrolyzable silicon is proposed toobtain a tack agent of high resistance to heat, wherein the grouptriggers a condensation reaction in the polymer of organic skeleton inwhich it is incorporated, to form the thermally stable siloxanecrosslinking.

Such a tack agent composition is disclosed by, e.g., Japanese PatentLaid-Open Publication No.71377/1984. This siloxane-crosslinking typetack agent has a disadvantage of poor relesability, as is the case withthe above-described silicone-based tack agent, in spite of its polymermain chain being essentially of organic skeleton. More concretely, whenit is adhered to a releasing paper or film coated with a silicone-basedreleasing agent, or when a laminate with the tack agent on one side ofthe base and silicone-based releasing agent on the other side is wound,exfoliation resistance between the tack agent and releasing paper orreleasing film increases with time, possibly breaking the releasingpaper when the worst comes to the worst, and making it impossible torelease the paper.

As is generally known, a silicone-based releasing paper frequentlyserves as the essential component of adhesive tapes, and the so-calledsilicone-based tack agent described above is not well separated from asilicone-based releasing paper. Although development of releasing papercoated with a non-silicone-based (e.g., fluorine-based) releasing agenthas been considered, application of the tack agent to releasing paper islimited, because it is not smoothly separated from the paper.

Japanese Patent Laid-Open Publication No.60771/1986 discloses a tackagent composition comprising (A) an organic polymer containing at leastone hydrolyzable silicon group in the molecule, (B) a tackifier resin,and (C) a specific organic zirconium or aluminum as the curing catalyst.It is developed in consideration of the actual situations that there isno tack agent composition high in resistance to heat and well releasablefrom a releasing paper coated with a silicone-based releasing agent. Thecomposition is said to be well releasable from a silicone-based paper orfilm.

However, further improvements in releasability and resistance to heathave been desired. Moreover, improvements in resistance to weather andcuring speed are left as the major technical problems to be solved.

Therefore, there are demands for a tack agent composition high inresistance to heat, well releasable from a releasing paper or the likecoated with a silicone-based releasing agent, and also high in curingspeed and resistance to weather.

(20) Japanese Patent Laid-Open Publication No.36395/1979 describes thata vinyl-based resin containing a hydrolyzable silyl group at theterminal or in the side chain is not only excellent in, e.g., gloss,resistance to weather and discoloration, but improved in adhesion toinorganic materials by the actions of the hydrolyzable silyl group, andforming a resin of dense network structures by crosslinking at roomtemperature with moisture, in particular that in air to have highhardness, and resistance to solvent, water, heat and weather.

According to Japanese Patent Laid-Open Publication No.63351/1982,however, the vinyl-based resin containing a hydrolyzable silyl group,although giving an excellent resin when cured in the presence of acuring catalyst, has a disadvantage of short pot life in the openatmosphere, in particular when the vinyl-based resin having 3hydrolyzable silyl groups contains the curing catalyst.

The above publication also describes the followings.

The inventions to improve the pot life in open atmospheres have beenalready applied for patents. For example, U.S. Pat. No. 4,043,953discloses an invention which improves pot life of a polymerized organicsilane in the presence of a curing catalyst, wherein the polymer isproduced by copolymerization of a monomer containing a CH₂═C< group,except the one containing an active hydrogen group, e.g., hydroxyl,carboxyl and amide group, with acrylate alkoxysilane, methacrylatealkoxysilane or vinyl alkoxysilane, and incorporated with ahydrolyzable, reactive silane monomer represented by the general formulaX_(n)Si(OR)_(4-n) (wherein, X is an organic group of 1 to 12 carbonatoms; R is methyl, ethyl, 2-methoxymethyl, 2-ethoxyethyl, or an alkylgroup having a carbon number of 5 or less; and “n” is an integer of 0 to2) at 0.5 to 15% by weight, based on the polymerized organic silane.

The curing catalysts useful for the above invention include an organicacid, e.g., p-toluene sulfonate and n-butyl phosphate; metallic salt oforgaic acid, e.g., tin naphthenate, dibutyl tin dilaurate, iron stearateand lead octenate; and organic amine, e.g., boron isodiamine, methylenediamine and imidazole at 0.1 to 5% by weight, preferably 0.2 to 1% byweight. However, the pot life was measured after the polymerized organicsilane, hydrolyzable, reactive silane monomer and curing catalyst werestored in a closed condition in the embodiments. The publication issilent on pot life in an open atmosphere, which is of practicalimportance. Indeed, pot life of the polymerized organic silane,hydrolyzable, reactive silane monomer and curing catalyst, as describedin the USP publication, in an open atmosphere is satisfactory only whenan organic amine is used, and short in the other cases. However, theresin cured in the presence of an organic amine has a disadvantage ofcoloration by the amine, and development of other catalysts has beendesired.

Japanese Patent Laid-Open Publication No.63351/1982 discloses acomposition of improved pot life, developed under the above situations.The publication discloses a composition of improved pot life, comprising

100 parts by weight of a vinyl-based silyl group containing resin withthe main chain essentially composed of a vinyl-based polymer and havingat least one silicon group bonded to a hydrolyzable group in themolecule at the terminal or in the side chain, and

0.01 to 10 parts by weight of a curing catalyst selected from the groupconsisting of a mercaptide type organotin compound having the Sn—S bond,a sulfide type organotin compound having the Sn═S bond, a mixture of acarboxylate type organotin compound and a mercaptide type organotincompound having the Sn—S bond, a mixture of a carboxylate type organotincompound and a sulfide type organotin compound having the Sn═S bond, amixture of a carboxylate type organotin compound and organic carboxylicacid, a mixture of a carboxylate type organotin compound and organiccarboxylate anhydride, and a mixture of an organic carboxylate compoundand organic carboxylate anhydride.

The above-described vinyl-based resin containing silyl group can beproduced by reacting a hydrosilane compound with a vinyl-based resinhaving the C—C double bond in the presence of a catalyst of Group VIIItransition metal. The publication describes that the vinyl-based resinuseful for the invention is not limited, except that it contains ahydroxyl group, and that the adequate resins include (meth)acrylateester, e.g., methyl (meth)acrylate, ethyl (meth)acrylate, butyl(meth)acrylate and 2-ethylhexyl (meth)acrylate; carboxylic acid, e.g.,(meth)acrylic acid, itaconic acid and fumaric acid; acid anhydride,e.g., maleic anhydride; epoxy compound, e.g., glycidyl (meth)acrylate;amino compound, e.g., diethylaminoethyl acrylate and aminoethyl vinylether; amide compound, e.g., (meth)acrylamide, amide itaconate,α-ethylacrylamide, crotonamide, diamide fumarate, diamide maleate andN-butoxymethyl (meth)acrylamide; and resin containing, as the mainingredient, a copolymer selected from the group consisting ofacrylonitrile, styrene, α-methyl styrene, vinyl chloride, vinyl acetate,vinyl propionate and the like.

Japanese Patent Laid-Open Publication No.63351/1982, however, is silenton ethylene/α-olefin/non-conjugated polyene random copolymer rubberproduced by copolymerization of ethylene, α-olefin of 3 to 20 carbonatoms and norbornene compound having vinyl group (═C═CH₂) at theterminal, instead of the vinyl-based resin.

Therefore, there are demands for a curable rubber composition composedof an ethylene/α-olefin/non-conjugated polyene random copolymer rubbercontaining a hydrolyzable silyl group at the terminal or in the sidechain and curing catalyst, improved in pot life in an open atmosphere,high in curing speed, and excellent in resistance to weather.

(21) A curable composition containing an organotin compound is alreadyknown, where the organotin compound is in the form of a saturatedhydrocarbon-based polymer having at least one silicon-containing groupwith hydroxyl or a hydrolyzable group bonded to the silicon atom andcrosslinkable by forming the siloxane bond (such a silicon-contaiinggroup is hereinafter referred to as reactive silicon group). However,such curable composition involves various problems, e.g., low in curingspeed, residual tackiness and insufficient curing of the thin film.

Japanese Patent Laid-Open Publication No.41360/1996 describes use of aspecific organotin compound in order to solve the above problems.However, the composition has been strongly desired to have furtherimproved curing speed. At the same time, improvement in resistance toweather has been left as the major problem to be solved.

Therefore, there are demands for a curable composition forming thethree-dimensional network structures with moisture in air, quickly curedinto the solid of rubber-like elasticity, and excellent resistance toweather.

(22) A saturated hydrocarbon-based polymer having at least one reactivesilicon group in the molecule is known to have interesting nature thatit is crosslinked with moisture or the like even at room temperature byforming the siloxane bond accompanied with the hydrolysis or the like ofthe reactive silicon group, to form a rubber-like cured product. Thepolymer is excellent in resistance to heat, water and weather, anduseful for sealants for laminated glass and elastic sealants forbuildings.

The sealant for laminated glass is required to have excellent non-primeradhesion,i.e., to be fast adhesive to various objects in the absence ofa primer. More recently, the above property has been required not onlyfor sealant for laminated glass but also for sealant for other purposes,e g., by elastic sealant for buildings, to improve applicationefficiency by dispensing with a primer. However, the sealant which usesthe above-described saturated hydrocarbon-based polymer containing areactive silicon group is insufficient in adhesion in the absence of aprimer. Moreover, it is not always satisfactory in curing speed andresistance to weather.

Therefore, there are demands for a curable rubber compositioncontaining, as the major ingredient, rubber containing a hydrolyzablesilyl group, high in curing speed, and excellent in adhesion to variousobjects and in resistance to weather.

(23) The vehicle bodies have been coated with an underbody coatingmaterial on the back side of the floor or sides for various purposes,e.g., prevention of damages by gravel or the like bounded back on arunning vehicle, rust prevention and damping to reduce vibration andnoise, and also with a body sealer on a place structurally difficult totreat for rust prevention, e.g., joint between the internal and externalplates, for prevention of rust by rainwater, moisture or the like. Vinylchloride sol has been used as the material suitable for the abovepurposes.

Recently, the coating material for vehicles is strongly required to havebetter functions, e.g., still improved rust-prevention and dampingeffects by the thinner film for reducing weight, and reduced vehiclebaking temperature or even dispensing with the baking step forresources- and energy-saving viewpoints.

Vinyl chloride sol, although inexpensive and meeting the minimumrequirements, has a disadvantage that sufficient rust-preventive effector resistance to chipping (or damage-preventive effect) may not berealized at low baking temperature, because of slow gelation. Moreover,its damping effect is inherently not very high, and tends to furtherdeteriorate as the coating film is required to be thinner.

Japanese Patent Laid-Open Publication No.41349/1996 discloses a coatingmaterial for vehicles comprising a saturated hydrocarbon-based polymerhaving a reactive silicon group as the crosslinking group. It isimproved in various properties, e.g., those related to low-temperaturebaking, rust prevention, resistance to chipping and damping as comparedwith vinyl chloride sol. Nevertheless, however, these properties arestill insufficient, in particular damping property being expected forfurther improvement. Improvements are also expected for curing speed andweather resistance of the coating film thereof.

Therefore, there are demands for a curable composition, e.g., coatingmaterial for vehicles, high in curing speed even at low bakingtemperature, fast curable, and forming the uniform, stable coating filmeven when it is thin, excellent in rust prevention, chipping resistance,damping properties and weather resistance.

(24) Many industries, e.g., building, automobile and electric applianceindustries, have been using a variety of sealants for joining similar ordissimilar materials in assembling/fabrication lines, and also for otherpurposes, e.g., reinforcement, repair and replacement. Sealants ofvarious curing modes or main chain structures have been proposed forspecific purposes. However, few sealants commonly used for laminatedglass satisfy all of resistance to weather and heat, non-pollutingproperty, low moisture-permeability and weather-resistant adhesion.Still less is the sealant having low-odor property, in addition to theabove.

For example, a polysulfide-based sealant now being used is insufficientin low moisture-permeability, although showing excellent weatherresistance, heat resistance and non-polluting properties, and cannot beused for single sealing independently.

It is also insufficient in weather-resistant adhesion, one of the mostimportant properties for sealing laminated glass, for heat rayreflective glass, which has been recently massively used forenergy-saving purposes. In laminated glass production, this may need anadditional step of removing a metallic coating film that reflects heatray before the glass is filled with the sealant. Moreover, it is alsoinsufficient in properties related to hot water-resistant adhesion andlow odor, leaving environmental problems in the laminated glassproduction process.

A condensing curing type silicone-based sealant, as another type ofsealant for laminated glass, is insufficient in non-polluting propertyand low moisture-permeability, although satisfying weather resistance,heat resistance, weather-resistant adhesion and low-odor properties, andcannot be used for single sealing independently.

Therefore, there are demands for a sealant for laminated glasssatisfying weather resistance, heat resistance, non-polluting, lowmoisture-permeability, weather-resistant adhesion and low-odorproperties, and also excellent in mechanical characteristics andproducible at low cost.

(25) Sealants for laminated glass fall into two general categories, forprimary and secondary sealing. A laminated glass unit is sealed at itsedges with one type of sealant (single sealing) or 2 types of sealantsfor primary and secondary sealing (dual sealing), depending on specificpurposes.

A butyl rubber-based hot melt resin (hereinafter sometimes referred toas hot melt butyl) is commonly used as a sealant for single sealing andprimary sealant for dual sealing. It has following characteristics.

Hot melt butyl is a solid or waxy polymer at room temperature, becomingfluid when heated at around 100 to 250° C. When used as an adhesive, itis adhered to various base surfaces after being molten by wetting thesesurfaces. In an actual laminated glass production process, hot meltbutyl is discharged from a dedicated applicator by which it is moltenunder heating, and solidified after it is applied as sealant temperaturerapidly decreases. Therefore, it is curable for a much shorter periodthan other reaction-curing type sealants, and hence can greatly reducethe curing period and facilitate sealant management and handling.Therefore, it will play a still more important role in the futurelaminated glass markets, because of its good workability tosimultaneously realize its reduced procurement periods and increasedproductivity.

However, single-sealed laminated glass, mainly using hot melt butyl, islow in structural strength and difficult to secure steam-barrierproperty at the laminated glass inside for extended periods. Therefore,it can find limited industrial applications, e.g., sealant for show caseunits, which are replaced in a relatively short cycle.

The secondary seal in a dual-sealed laminated glass is low insteam-barrier property, although high in mechanical characteristics(e.g., adhesion to the glass), and needs primary sealing. Therefore, itis structured to block steam passing through the secondary seal by hotmelt butyl. This dual-sealed laminated glass needs 2 types of sealantsin the production process, and is more costly, although having longerserviceability, than the single-sealed type. Even a dual-sealedlaminated glass cannot sustain primary sealing, when the secondary sealis aged, possibly deteriorated to the single-sealed glass grade.

Adhesion of hot melt butyl depends on tackiness of butyl rubber, and ispossibly deteriorated by embrittlement at low temperature. Moreover, thesealant is thermoplastic at high temperature, possibly its softening tocause deviation of the laminate components from each other, andhence isrequired to be resistant to creeping at high temperature to prevent theabove problems.

Comparing thermoplastic hot melt butyl with the reaction-curing typesealant (e.g., polysulflde-based or silicone-based sealant), the formerhas at present major disadvantages of significant fluctuations ofproperties, e.g., mechanical properties, with temperature, although muchbetter in workability. Therefore, it tends to have narrower applicableareas in terms of glass size and weight than the reaction-curing type.

Therefore, there are demands for a sealant for laminated glass, improvedin temperature-dependence of structural strength and adhesion to a basematerial, while keeping steam-barrier characteristics of hot melt butyl,and suitable as the sealant for laminated glass for primary sealing fordual sealing or single sealing.

The present invention has the following objects.

(1) The present invention is intended to solve the problems involved inthe conventional technologies (1) described above. Accordingly, it is anobject of the present invention to provide a curable elastic composition(curable rubber composition) improved in elongation of the cured productand residual tackiness, in its surface and, at the same time, high incuring speed and capable of giving the cured product of high resistanceto weather, and also to provide use of the same.

(2) The present invention is also intended to solve the problemsinvolved in the conventional technologies (2) described above.Accordingly, it is another object of the present invention to provide acurable rubber composition containing, as the main ingredient, asilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber which has a structural unit derived from a norbornenecompound as the non-conjugated polyene with a specific vinyl group atthe terminal and containing a specific hydrolyzable silyl group in themolecule, and high in curable speed and excellent in adhesion to avariety of objects and resistance to weather, and also to provide use ofthe same.

(3) The present invention is also intended to solve the problemsinvolved in the conventional technologies (3) described above.Accordingly, it is still another object of the present invention toprovide a curable composition high in curing speed, leaving littleresidual tackiness on the cured product surface, after it is cured,highly resistant to weather, showing high adhesion between a paint andsealant surface, when the former is applied, and useful for sealant,primer or the like.

(4) The present invention is also intended to solve the problemsinvolved in the conventional technologies (4) described above.Accordingly, it is still another object of the present invention toprovide a curable composition containing a rubber-based organic polymerhaving a reactive silicon group, which is rapidly cured with moisture,excellent in tensile-related properties, capable of giving a rubber-likeelastomer free of residual tackiness on the surface, and improved inresistance to weather and storage stability.

(5) The present invention is also intended to solve the problemsinvolved in the conventional technologies (5) described above.Accordingly, it is still another object of the present invention toprovide a rubber composition curable at room temperature, high in curingspeed, excellent in resistance to weather, and capable of giving thehighly adhesive cured product, and also to provide use of the same.

(6) The present invention is also intended to solve the problemsinvolved in the conventional technologies (6) described above.Accordingly, it is still another object of the present invention toprovide a curable rubber composition, easily cured with moisture in airat room temperature or under heating, and at high speed, and excellentin resistance to weather.

(7) The present invention is also intended to solve the problemsinvolved in the conventional technologies (7) described above.Accordingly, it is still another object of the present invention toprovide a curable composition high in curing speed, giving aweather-resistant cured product, and suitable for adhesive, sealant orthe like.

(8) The present invention is also intended to solve the problemsinvolved in the conventional technologies (8) described above.Accordingly, it is still another object of the present invention toprovide a curable composition quickly cured when it is used, even afterbeing stored for extended periods, and giving a weather-resistant curedproduct.

(9) The present invention is also intended to solve the problemsinvolved inthe conventional technologies (9) described above.Accordingly, it is still another object of the present invention toprovide a curable rubber composition high in storage stability andcuring speed, and giving a highly weather-resistant cured product, andalso to provide use of the same.

(10) The present invention is also intended to solve the problemsinvolved in the conventional technologies (10) described above.Accordingly, it is still another object of the present invention toprovide a new curable rubber composition which incorporates a hydrate ofmetallic salt as the moisture source, and also to provide use of thesame.

It is still another object of the present invention to provide a curablerubber composition showing no increase in viscosity while being stored,high in curing speed and resistance to weather, and also to provide useof the same.

It is still another object of the present invention to provide a curablerubber composition which can incorporate a compound having a reactivesilicon group readily reactive with moisture, e.g., silane couplingagent, and also to provide use of the same.

(11) The present invention is also intended to solve the problemsinvolved in the conventional technologies (11) described above.Accordingly, it is still another object of the present invention toprovide a composition low in viscosity, good in workability, sufficientin curing speed, excellent in, e.g., resistance to weather, heat andwater, and capable of giving a rubber-like cured product high instrength and elongation (low modulus of elasticity).

(12) The present invention is also intended to solve the problemsinvolved in the conventional technologies (12) described above.Accordingly, it is still another object of the present invention toprovide a rubber composition high in vulcanization speed, improved inresistance to weather and excellent in mechanical strength, whileretaining the various favorable characteristics of anethylene/α-olefin/non-conjugated polyene random copolymer rubber, e.g.,excellent resistance to heat and chemicals of the vulcanized product.

(13) The present invention is also intended to solve the problemsinvolved in the conventional technologies (13) described above.Accordingly, it is still another object of the present invention toprovide a rubber composition high in adhesion; giving the cured productwith greatly changed layered structures, low in elasticity and high inelongation; giving the cured product dispersed with an epoxy resin whosecontent in the matrix increases as its particle size decreases, and highin modulus of elasticity and tensile shear strength; sufficiently highin curing speed, and giving the cured product of high resistance toweather, and also to provide a method of producing the same.

(14) The present invention is also intended to solve the problemsinvolved in the conventional technologies (14) described above.Accordingly, it is still another object of the present invention toprovide a curable rubber composition improved in toughness and strength,giving the cured product of high strength irrespective of moisturequantity, and, at the same time, high in curing speed and giving thecured product of high resistance to weather.

(15) The present invention is also intended to solve the problemsinvolved in the conventional technologies (15) described above.Accordingly, it is still another object of the present invention toprovide a rubber composition well-balanced between workability andmechanical properties of the cured product, sufficient in curing speedand resistance to weather of the cured product, and suitable as asealant for laminated glass.

(16) The present invention is also intended to solve the problemsinvolved in the conventional technologies (16) described above.Accordingly, it is still another object of the present invention toprovide a curable composition high in curing speed, giving the curedproduct of high resistance to weather, and suitable for adhesives andsealants.

(17) The present invention is also intended to solve the problemsinvolved in the conventional technologies (17) described above.Accordingly, it is another object of the present invention to provide acurable rubber composition containing, as the main ingredient, asilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber which has a structural unit derived from a norbornenecompound with a specific vinyl group at the terminal as thenon-conjugated polyene and containing a hydrolyzable silyl group in themolecule, and giving the cured product excellent in resistance toweather and heat, and also to provide use of the same.

(18) The present invention is also intended to solve the problemsinvolved in the conventional technologies (18) described above.Accordingly, it is still another object of the present invention toprovide a curable rubber composition containing, as the main ingredient,a saturated hydrocarbon-based polymer having a reactive silicon group,which is highly adhesive to various materials, improved inweather-resistant adhesion for various types of glass, in particularheat ray reflective glass, and excellent in resistance to weather andcuring speed.

(19) The present invention is also intended to solve the problemsinvolved in the conventional technologies (19) described above.Accordingly, it is still another object of the present invention toprovide a tack agent composition high in resistance to heat, wellreleasable from a releasing paper or the like coated with asilicone-based releasing agent, and also high in curing speed andresistance to weather, and also to provide use of the same.

(20) The present invention is also intended to solve the problemsinvolved in the conventional technologies (20) described above.Accordingly, it is still another object of the present invention toprovide a rubber composition composed of anethylene/α-olefin/non-conjugated polyene random copolymer rubbercontaining a hydrolyzable silyl group at the terminal or in the sidechain and a curing catalyst, improved in pot life in an open atmosphere.

It is still another object of the present invention to provide a curablerubber composition high in curing speed and excellent in resistance toweather, and also to provide use of the same.

(21) The present invention is also intended to solve the problemsinvolved in the conventional technologies (21) described above.Accordingly, it is still another object of the present invention toprovide a new curable composition forming the three-dimensional networkstructures with moisture in air, quickly cured into the solid ofrubber-like elasticity, and excellent resistance to weather.

(22) The present invention is also intended to solve the problemsinvolved in the conventional technologies (22) described above.Accordingly, it is still another object of the present invention toprovide a curable rubber composition containing, as the majoringredient, an ethylene/α-olefin/non-conjugated polyene random copolymerrubber containing a hydrolyzable silyl group, high in curing speed, andexcellent in adhesion to various objects and in resistance to weather.

(23) The present invention is also intended to solve the problemsinvolved in the conventional technologies (23) described above.Accordingly, it is still another object of the present invention toprovide a curable composition, e.g., coating material for vehicles, highin curing speed even at low baking temperature, fast curable, andforming the uniform, stable coating film even when it is thin, excellentin rust prevention, chipping resistance, damping properties andresistance to weather.

(24) The present invention is also intended to solve the problemsinvolved in the conventional technologies (24) described above.Accordingly, it is still another object of the present invention toprovide a sealant for laminated glass satisfying weather resistance,heat resistance, non-polluting, low moisture-permeability,weather-resistant adhesion and low-odor properties, and also excellentin mechanical characteristics and producible at low cost.

(25) The present invention is also intended to solve the problemsinvolved in the conventional technologies (25) described above.Accordingly, it is still another object of the present invention toprovide a sealant for laminated glass, improved intemperature-dependence of structural strength and adhesion to a basematerial, while keeping steam-barrier characteristics of hot melt butyl,and suitable as the sealant for laminated glass for primary sealing fordual sealing or single sealing.

DISCLOSURE OF THE INVENTION

The curable composition of the present invention is characterized inthat it contains

a silyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1) which has a structural unit derived from anorbornene compound, represented by the following general formula [I] or[II], with at least one specific vinyl group at the terminal, as thenon-conjugated polyene and containing a hydrolyzable silyl group,represented by the following general formula [III] in the molecule, and

a compound (B), other than the rubber (A1), having hydroxyl and/or ahydrolyzable group.

wherein, “n” is an integer of 0 to 10;

-   R¹ is hydrogen atom or an alkyl group of 1 to 10 carbon atoms; and-   R² is hydrogen atom or an alkyl group of 1 to 5 carbon atoms.

wherein, R³ is hydrogen atom or an alkyl group of 1 to 10 carbon atoms.

wherein, R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; Xis a hydrolyzable group selected from the group consisting of hydride,halogen, alkoxyl, acyloxy, ketoximate, amide, acid amide, aminoxy,mercapto, alkenyloxy, thioalkoxy and amino group; and “a” is an integerof 0 to 2.

The compound (B) having hydroxyl and/or a hydrolyzable group ispreferably a silicon-containing compound.

The curable compositions of the present invention include thefollowings.

(1) A curable elastic composition characterized in that it contains

-   -   the silyl-containing ethylene/α-olefin/non-conjugated polyene        random copolymer rubber (A1), and    -   a compound having a silanol group and/or a compound which can        react with moisture to form a compound having a silanol group in        the molecule (B1).

(2) A curable rubber composition characterized in that it contains

-   -   the silyl-containing ethylene/α-olefin/non-conjugated polyene        random copolymer rubber (A1), and    -   a tetravalent tin compound (C), and    -   a silicon compound (B2) represented by the following general        formula [V]:        R⁴ _(a)Si(OR⁵)_(4-a)  [V]        wherein, R⁴ and R⁵ are each a hydrocarbon group of 1 to 20        carbon atoms which may be substituted or not substituted, and        “a” is 0, 1, 2, or 3.

(3) A curable composition characterized in that it contains

-   (a) the silyl-containing ethylene/α-olefin/non-conjugated polyene    random copolymer rubber (A1), and-   (b) a silicon compound (B3) having at least one amino group and at    least one trialkylsiloxy group in the molecule.

(4) A curable composition characterized in that it contains

-   (a) the silyl-containing ethylene/α-olefin/non-conjugated polyene    random copolymer rubber (A1), and-   (b) an organosilicon compound (B4) represented by the following    general formula [VI]:    (R²(CH₃)₂SiO)_(n)R¹  [VI]    wherein, R¹ is an alcohol residue or weak acid residue, R² is methyl    or vinyl group, and “n” is a positive integer.

(5) A rubber composition curable at room temperature, characterized inthat it contains

-   -   the silyl-containing ethylene/α-olefin/non-conjugated polyene        random copolymer rubber (A1), and    -   a silane compound (B5) represented by one of the following        general formulae [VII-1] to [VII-6]:

wherein, R⁴ is a monovalent hydrocarbon group of 1 to 10 carbon atoms,selected from the group consisting of alkyl, aralkyl and aryl;

-   -   X is a group selected from the group consisting of halogen,        hydroxy, alkoxyl, acyloxy, aminoxy, phenoxy, thioaikoxy, amino,        ketoximate, mercapto and alkenyloxy;    -   R⁵ is an alkylene or arylene group of 8 to 200 carbon atoms; R⁶        is a monovalent alkyl group of 8 to 200 carbon atoms; and “n” is        an integer of 0 to 2.

(6) A curable rubber composition, characterized in that it contains, asthe active ingredients,

-   -   the silyl-containing ethylene/α-olefin/non-conjugated polyene        random copolymer rubber (A1),    -   (D) amines selected from the group consisting of aliphatic        amines, alicyclic amines, modified cycloaliphatic polyamines and        ethanol amines,    -   (B6) a silane coupling agent represented by the general formula        Y₃(Si)Z, wherein Y is an alkoxyl group; and Z is an alkyl group        containing a functional group selected fromthe group consisting        of amino group, which maybe substituted with an aminoalkyl group        or not, and mercapto group, and    -   (E) a resin composed of a lacquer-based paint, an acrylic        lacquer-based paint, an acrylic resin-based paint, a        thermosetting acrylic paint, an alkyd paint, a melamine paint,        an epoxy paint or organopolysiloxane.

(7) A curable composition, characterized in that it contains

-   -   (a) the silyl-containing ethylene/α-olefin/non-conjugated        polyene random copolymer rubber (A1), and    -   (b) a silane-based compound substituted with amino group (B7)

(8) A curable composition, characterized in that it contains

-   -   the silyl-containing ethylene/α-olefin/non-conjugated polyene        random copolymer rubber (A1), and    -   a filler (F), a plasticizer (G), a curing catalyst (H) and an        organocarboxylate compound (B8).

(9) A curable rubber composition, characterized in that it contains

-   -   the silyl-containing ethylene/α-olefin/non-conjugated polyene        random copolymer rubber (A1),    -   alcohols (B9), and/or a hydrolyzable ester compound (I) (except        a hydrolyzable organosilicon compound (B10)), and    -   a hydrolyzable organosilicon compound (B10).

(10) A two- or multi-liquid type curable rubber composition composed ofat least two liquids, characterized in that it contains

-   -   a major ingredient (I) containing the silyl-containing        ethylene/α-olefin/non-conjugated polyene random copolymer rubber        (A1), and a curing agent (II) containing,    -   a silanol condensing catalyst (J) and water or a hydrate of a        metallic salt (B11).

Each of the curable compositions (1) to (10) may contain thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A2), described later, in place of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1).

The other curable compositions of the present invention arecharacterized in that they contain, in the molecule, thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A2) containing a hydrolyzable silyl group, representedby the following general formula (1), and a high-molecular compound (K)other than the rubber (A2) and/or an inorganic filler (L):

wherein, R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; Xis a hydrolyzable group selected from the group consisting of hydride,halogen, alkoxyl, acyloxy, ketoximate, amide, acid amide, aminoxy,thioalkoxy, amino, mercapto and alkenyloxy group; and “m” is an integerof 0 to 2.

These curable compositions include the followings.

(11) A rubber composition, characterized in that it contains thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A2), and an organosilicon polymer (K1)

(12) A rubber composition, characterized in that it contains thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A2), an organic rubber (K2) and a crosslinking agent(M) for the organic rubber (K2).

(13) A rubber composition, characterized in that it contains thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A2), an epoxy resin (K3), a silane coupling agent (N),a silanol condensing catalyst (O), and a curing agent (P) for the epoxyresin.

(14) A rubber composition, characterized in that it contains thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A2), an epoxy resin (K3), a silicon compound (Q)containing a hydrolyzable silyl group and a functional group reactivewith the epoxy group in the molecule, and a silicon compound (R)containing at least two hydroxyl groups bonded to the silicon atom inthe molecule.

(15) A rubber composition, characterized in that it contains thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A2), calcium carbonate (L1), and talc (L2).

In the compositions (11) to (15), the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A2)normally has at least one type of silyl groups represented by thefollowing general formula (2) or (3):

wherein, R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; R¹is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; R² is ahydrogen atom or an alkyl group of 1 to 5 carbon atoms; R³ is a hydrogenatom or an alkyl group of 1 to 10 carbon atoms; X is a hydrolyzablegroup selected from the group consisting of hydride, halogen, alkoxyl,acyloxy, ketoximate, amide, acid amide, aminoxy, thioalkoxy, amino,mercapto and alkenyloxy group; and “m” is an integer of 0 to 2 and “n”is an integer of 0 to 10.

It is particularly preferable that the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A2) isproduced by reacting an ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber having a norbornene compound with at least one terminalvinyl group as the non-conjugated polyene represented by the followinggeneral formula (4) and/or (5):

wherein, R¹ is a hydrogen atom or an alkyl group of 1 to 10 carbonatoms; R² is a hydrogen atom or an alkyl group of 1 to 5 carbon atoms;R³ is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; and “n”is an integer of 0 to 10, with a silicon compound represented by thefollowing general formula (6):

wherein, R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; Xis a hydrolyzable group selected from the group consisting of hydride,halogen, alkoxyl, acyloxy, ketoximate, amide, acid amide, aminoxy,thioalkoxy, amino, mercapto and alkenyloxy group; and “m” is an integerof 0 to 2, to add the SiH group in the silicon compound to the doublebond of the copolymer rubber.

Each of the curable compositions (11) to (15) may contain thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1) in place of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A2).

The other curable compositions of the present invention arecharacterized in that they contain the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1)and a stabilizer.

(16) A curable composition, characterized in that it contains

-   (a) the silyl-containing ethylene/α-olefin/non-conjugated polyene    random copolymer rubber (A1), (b) a nickel-containing light    stabilizer (S) and (C) a silane coupling agent (T).

(17) A curable rubber composition, characterized in that it contains thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1), and a sulfur-based aging inhibitor (U).

(18) A curable composition, characterized in that it contains thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1), and a compound (V) having, in the molecule, anunsaturated group capable of triggering polymerization by reacting withoxygen in air and/or a photopolymerizable material.

Each of the curable compositions (16) to (18) may contain thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A2) in place of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1).

The other curable compositions of the present invention arecharacterized in that they contain the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1)and a silanol catalyst.

(19) A tackifier composition, characterized in that it contains thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1),

-   a tackifier resin (W), and-   a curing catalyst (H) comprising an organozirconium compound (H1)    represented by the following general formula [VIII] or an    organoaluminum compound (H2) represented by the following general    formul [IX]:

wherein, “n” is an integer of 0 to 4,

-   -   R is a monovalent hydrocarbon group of 1 to 20 carbon atoms, and    -   Y is a group selected from the group consisting of hydrocarbon        of 1 to 8 carbon atoms, halogenated hydrocarbon, cyanoalkyl,        alkoxyl, halogenated alkoxyl, cyanoalkoxy and amino group, which        may be the same or different, and

wherein, “p” is an integer of 0 to 3,

-   -   R is a monovalent hydrocarbon group of 1 to 20 carbon atoms, and    -   Y is a group selected from the group consisting of hydrocarbon        of 1 to 8 carbon atoms, halogenated hydrocarbon, cyanoalkyl,        alkoxyl, halogenated alkoxyl, cyanoalkoxy and amino group, which        may be the same or different.

(20) A rubber composition of improved pot life, characterized in that itcontains

-   -   the silyl-containing ethylene/α-olefin/non-conjugated polyene        random copolymer rubber (A1),    -   a curing catalyst (H) composed of a mercaptide type organotin        compound (H3) having the Sn—S bond, a sulfide type organotin        compound (H4) having the Sn═S bond, organocarboxylic acid (H5),        organocarboxylic anhydride (H6), or a mixture of one of the        above compounds and a carboxylic type organotin compound (H7).

(21) A curable composition, characterized in that it contains

-   -   the silyl-containing ethylene/α-olefin/non-conjugated polyene        random copolymer rubber (A1), and    -   a compound (H8) as the curing catalyst (H), represented by the        general formula Q₂Sn(OZ)₂ or [Q₂Sn(OZ)]₂O,        wherein, Q is a monovalent hydrocarbon group of 1 to 20 carbon        atoms; and Z is a monovalent hydrocarbon group of 1 to 20 carbon        atoms or organic group having a functional group capable of        forming therein a coordination bond with Sn.

(22) A curable rubber composition, characterized in that it contains thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1), and

-   -   titanates (Y)

Each of the curable compositions (19) to (22) may contain thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A2) in place of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1).

The other curable compositions of the present invention include thefollowings.

They are crosslinkable rubber compositions composed of an organicpolymer (Z) containing a hydrolyzable silyl group represented by thefollowing general formula [III] and essentially no unsaturated doublebond in the main chain, and a compound (B), preferably a siliconcontaining compound, containing a hydroxyl and/or a hydrolyzable group;and used for electric/electronic device members, transportationmachines, and civil engineering/construction, medical and leisure areas:

wherein, R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; Xis a hydrolyzable group selected from the group consisting of hydride,halogen, alkoxyl, acyloxy, ketoximate, amide, acid amide, aminoxy,mercapto, alkenyloxy, thioalkoxy and amino group; and “a” is an integerof 0 to 2.

More concretely, these compositions include the followings.

(1) A curable elastomer composition, which is a crosslinkable rubbercomposition characterized in that it is composed of

-   -   the organic polymer (Z) and    -   a compound having a silanol group in the molecule and/or a        compound which can react with moisture to form a compound having        a silanol group in the molecule (B1), and        is used for electric/electronic device members, transportation        machines, and civil engineering/construction, medical and        leisure areas.

(2) A curable rubber composition, which is a crosslinkable andcharacterized in that it contains

-   -   the organic polymer (Z),    -   a tetravalent tin compound (C) and    -   a silicon compound (B2), and        is used for electric/electronic device members, transportation        machines, and civil engineering/construction, medical and        leisure areas.

(3) A curable composition, characterized in that it contains

-   (a) the organic polymer (Z) and-   (b) a silicon compound (B3) having at least one amino group and at    least one trialkylsiloxy group in the molecule, and is used for    electric/electronic device members, transportation machines, and    civil engineering/construction, medical and leisure areas.

(4) A curable composition, characterized in that it contains

-   (a) the organic polymer (Z) and-   (b) an organosilicon compound (B4) represented by the following    general formula [VI]:    (R²(CH₃)₂SiO)_(n)R¹  [VI]    wherein, R¹ is an alcohol residue or weak acid residue, R² is methyl    or vinyl group, and “n” is a positive integer, and is used for    electric/electronic device members, transportation machines, and    civil engineering/construction, medical and leisure areas.

(5) A rubber composition, which is curable at room temperaturecrosslinkable, characterized in that it contains

-   -   the organic polymer (Z) and    -   a silane compound (B5), and        is used for electric/electronic device members, transportation        machines, and civil engineering/construction, medical and        leisure areas.

(6) A curable rubber composition which is crosslinkable, characterizedin that it contains, as the active ingredients,

-   -   the organic polymer (Z),    -   amines (D) selected from the group consisting of aliphatic        amines, alicyclic amines, modified cycloaliphatic polyamines and        ethanol amines,    -   a silane coupling agent (B6) represented by the general formula        Y₃(Si)Z, wherein Y is an alkoxyl group; and Z is an alkyl group        containing a functional group selected from the group consisting        of amino group, which may be substituted with an aminoalkyl        group or not, and mercapto group, and    -   a resin (E) composed of a lacquer-based paint, an acrylic        lacquer-based paint or an acrylic resin-based paint, or a        thermosetting acrylic paint, an alkyd paint, a melamine paint,        an epoxy paint or organopolysiloxane, and    -   is used for electric/electronic device members, transportation        machines, and civil engineering/construction, medical and        leisure areas.

(7) A curable composition, characterized in that it contains

-   -   (a) the organic polymer (Z) and    -   (b) a silane-based compound substituted with amino group (B7),        and    -   is used for electric/electronic device members, transportation        machines, and civil engineering/construction, medical and        leisure areas.

(8) A curable composition, characterized in that it contains the organicpolymer (Z), a filler (F), aplasticizer (G), a curing catalyst (H) andan organocarboxylate compound (B8), and is used for electric/electronicdevice members, transportation machines, and civilengineering/construction, medical and leisure areas.

(9) A curable rubber composition, characterized in that it iscrosslinkable and contains

-   -   the organic polymer (Z),    -   alcohols (B9), and/or a hydrolyzable ester compound (I) (except        the hydrolyzable organosilicon compound (B10) and    -   a hydrolyzable organosilicon compound (B10), and is used for        electric/electronic device members, transportation machines, and        civil engineering/construction, medical and leisure areas.

(10) A two- or multi-liquid type curable crosslikable rubber compositioncomposed of at least two liquids, characterized in that it contains

-   -   the major ingredient (I) containing the organic polymer (Z)    -   a curing agent (II) containing    -   a silanol condensing catalyst (J) and water or a hydrate of    -   a metallic salt (B11), and        is used for electric/electronic device members, transportation        machines, and civil engineering/construction, medical and        leisure areas.

The rubber compositions of the present invention are crosslinkable onescomposed of an organic polymer (Z1) containing a hydrolyzable silylgroup represented by the following general formula (1) and essentiallyno unsaturated double bond in the main chain, a high-molecular compound(K) other than the polymer (Z1) and/or an inorganic filler (L), and

used for electric/electronic members, transportation machines, and civilengineering/construction, medical and leisure areas:

wherein, R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; Xis a hydrolyzable group selected from the group consisting of hydride,halogen, alkoxyl, acyloxy, ketoximate, amide, acid amide, aminoxy,thioalkoxy, amino, mercapto and alkenyloxy group; and “m” is an integerof 0 to 2.

These rubber compositions include the followings:

(11) A rubber composition, which is crosslinkable and characterized inthat it contains the organic polymer (Z1) and an organosilicon polymer(K1), and

is used for electric/electronic device members, transportation machines,and civil engineering/construction, medical and leisure areas.

(12) A rubber composition, which is crosslinkable and characterized inthat it contains the organic polymer (Z1), organic rubber (K2) and acrosslinking agent (M) for the organic rubber (K2), and

is used for electric/electronic device members, transportation machines,and civil engineering/construction, medical and leisure areas.

(13) A rubber composition, which is crosslinkable and characterized inthat it contains the organic polymer (Z1), an epoxy resin (K3), a silanecoupling agent (N), a silanol condensing catalyst (O) and a curing agent(P) for the epoxy resin, and

is used for electric/electronic device members, transportation machines,and civil engineering/construction, medical and leisure areas.

(14) A rubber composition, which is crosslinkable and characterized inthat it contains

-   -   the organic polymer (Z1),    -   an epoxy resin (K3),    -   a silicon compound (Q) containing a functional group reactive        with the epoxy group and hydrolyzable silyl group in the        molecule and    -   a silicon compound (R) containing at least two hydroxyl groups        bonded to the silicon atom in the molecule, and        is used for electric/electronic device members, transportation        machines, and civil engineering/construction, medical and        leisure areas.

(15) A rubber composition, which is crosslinkable and characterized inthat it contains the organic polymer (Z1), calcium carbonate (L1) andtalc (L2), and

is used for electric/electronic device members, transportation machines,and civil engineering/construction, medical and leisure areas.

(16) A curable composition, characterized in that it contains (a) theorganic polymer (Z), (b) a nickel-containing light stabilizer (S) and asilane coupling agent (T), and is used for electric/electronic devicemembers, transportation machines, and civil engineering/construction,medical and leisure areas.

(17) A rubber composition, which is crosslinkable and characterized inthat it contains the organic polymer (Z) and a sulfur-based aginginhibitor (U), and

is used for electric/electronic device members, transportation machines,and civil engineering/construction, medical and leisure areas.

(18) A curable composition, characterized in that it contains theorganic polymer (Z), and a compound (V) having, in the molecule, anunsaturated group capable of triggering polymerization by reacting withoxygen in air and/or photopolymerizable material, and

is used for electric/electronic device members, transportation machines,and civil engineering/construction, medical and leisure areas.

(19) A tackifier composition, which is a crosslinkable rubbercomposition and characterized in that it contains

-   -   the organic polymer (Z),    -   a tackifier resin (W) and    -   a curing catalyst (H) composed of an organozirconium compound        (H1) or an organoaluminum compound (H2), and        is used for electric/electronic device members, transportation        machines, and civil engineering/construction, medical and        leisure areas.

(20) A rubber composition, which is crosslinkable and characterized inthat it contains

-   -   the organic polymer (Z) and    -   a curing catalyst (H) composed of a mercaptide type organotin        compound (H3) having the Sn—S bond, a sulfide type organotin        compound (H4) having the Sn═S bond, organocarboxylic acid (H5),        organocarboxylic anhydride (H6), or a mixture of one of the        above compounds and a carboxylic type organotin compound (H7),        and is used for electric/electronic device members,        transportation machines, and civil engineering/construction,        medical and leisure areas.

(21) A curable composition, characterized in that it contains

-   -   the organic polymer (Z) and    -   a compound (H8) as the curing catalyst (H), represented by the        general formula Q₂Sn(OZ)₂ or [Q₂Sn(OZ)]₂O,        wherein, Q is a monovalent hydrocarbon group of 1 to 20 carbon        atoms; and Z is a monovalent hydrocarbon group of 1 to 20 carbon        atoms or an organic group having a functional group capable of        forming therein a coordination bond with Sn, and        is used for electric/electronic device members, transportation        machines, and civil engineering/construction, medical and        leisure areas.

(22) A curable rubber composition, characterized in that it contains

-   -   the organic polymer (Z) and titanates (Y), and        is used for electric/electronic device members, transportation        machines, and civil engineering/construction, medical and        leisure areas.

(23) A curable composition, characterized in that it contains thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1), and

is used for electric/electronic device members, transportation machines,and civil engineering/construction, medical and leisure areas.

In the above curable composition (23), the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A2)may be used in place of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1).

The electric/electronic device members for which the composition of thepresent invention can be used include those for heavy electricalequipments, electronic devices, sealants for electric/electronic devicecircuits and substrates, potting materials, coating materials andadhesives, repair materials for wire coatings, insulation sealants forwire joint members, rolls for OA devices, vibration absorbers, andsealants for gel and condensers.

The sealants can go into refrigerators, freezers, washing machines, gasmeters, microwave ovens, steam irons and leakage breakers, among others.

The potting materials can go into high-voltage transformer circuits,printed circuit boards, high-voltage transformers equipped with avariable resistance, electric insulators, semiconductor devices,electroconductive devices, solar batteries and flyback transformers forTV sets, among others.

The coating materials can be used for coating thick-wall resistors forhigh-voltage services and circuit elements for hybrid ICs; HICs;electrical insulator members; semiconductor members, electroconductivemembers; modules; printed circuits; ceramic substrates; buffers fordiodes, transistors and bonding wires; semiconductor devices; andoptical fibers for optical communications, among others.

The adhesives can be used for adhesion of CRT wedges, necks, electricalinsulator members, semiconductor members and electroconductive members,among others.

The transportation machines in which the compositions of the presentinvention can go into include vehicles, ships, aircraft and railwayvehicles.

More concretely, the compositions of the present invention can be usedfor the following areas. They can go into vehicles as sealants forengine gaskets, electrical members and oil filters; as potting materialsfor igniter HICs and hybrid ICs; as coating materials for bodies, windowpanes and engine controller substrates; and as adhesives for oil pangaskets, timing cover belts, braids, head lamp lenses, sunroof seals andmirrors, among others.

They can also go into ships as sealants for wiringconnecting/distribution boxes, electrical system members and wires; andadhesives for wires and glass, among others.

They can also go into the civil engineering/construction areas assealants for building materials, e.g., butt joints in the glassscreening method for commercial buildings, joints around glass betweensashes, joints for interiors in bathrooms, toilets and showcases, jointsin bath tubs, flexible joints in exteriors of prefabricated housings,and joints for sizingboards; sealants for laminated glass; sealants forcivil engineering works, e.g., for repairing roads; paints/adhesives formetals, glass, stone materials, slates, concrete and tiles; and adhesivesheets, waterproof sheets and vibration-preventive sheets, among others.

They can also go into medical areas, e.g., sealants for rubber plugs formedicinal purposes, syringe gaskets and rubber plugs for decompressionedblood tubes.

They can also go into leisure areas, e.g., swimming caps, diving masksand earplugs for swimming; and gel buffers for sporting shoes andbaseball gloves.

The major areas the curable compositions of the present invention can gointo are sealants, potting agents, coating materials and adhesives.

The curable compositions for sealants, potting agents, coating materialsand adhesives include the crosslinkable rubber compositions composed ofthe organic polymer (Z) and a compound (B), preferablysilicon-containing compound, having a hydroxyl and/or a hydrolyzablegroup.

More concretely, these compositions include the followings.

(1)′ A sealant, a potting agent, a coating material or an adhesive,characterized in that it is composed of a crosslinkable rubbercomposition, containing

-   -   the organic polymer (Z) and    -   a compound having a silanol group in the molecule and/or the        compound which can react with moisture to form a compound having        a silanol group in the molecule (B1).

(2)′ A sealant, a potting agent, a coating material or an adhesive,characterized in that it is composed of a crosslinkable rubbercomposition, containing

-   -   the organic polymer (Z),    -   a tetravalent tin compound (C) and    -   a silicon compound (B2).

(3)′ A sealant, a potting agent, a coating material or an adhesive,characterized in that it is composed of a curable composition,containing

-   (a) the organic polymer (Z) and-   (b) a silicon compound (B3) having at least one amino group and at    least one trialkylsiloxy group in the molecule.

(4)′ A sealant, a potting agent, a coating material or a adhesive,characterized in that it is composed of a curable composition,containing

-   (a) the organic polymer (Z) and-   (b) an organosilicon compound (B4) represented by the following    general formula [VI]:    (R²(CH₃)₂SiO)_(n)R¹  [VI]    wherein, R¹ is an alcohol residue or weak acid residue, R² is methyl    or vinyl group, and “n” is a positive integer.

(5)′ A sealant, a potting agent, a coating material or an adhesive,characterized in that it is composed of a crosslinkable rubbercomposition, containing

-   -   the organic polymer (Z) and    -   a silane compound (B5).

(6)′ A sealant, a potting agent, a coating material or an adhesive,characterized in that it is composed of a crosslinkable rubbercomposition, containing, as the active ingredients,

-   -   the organic polymer (Z),    -   amines (D) selected from the group consisting of aliphatic        amines, alicyclic amines, modified cycloaliphatic polyamines and        ethanol amines,    -   a silane coupling agent (B6) represented by the general formula        Y₃(Si)Z, wherein Y is an alkoxyl group; and Z is an alkyl group        containing a functional group selected from the group consisting        of amino group, which maybe substituted with an aminoalkyl group        or not, and mercapto group, and    -   a resin (E) composed of a lacquer-based paint, an acrylic        lacquer-based paint or an acrylic resin-based paint, or a        thermosetting acrylic paint, an alkyd paint, a melamine paint,        an epoxy paint or organopolysiloxane.

(7)′ A sealant, a potting agent, a coating material or an adhesive,characterized in that it is composed of a curable composition,containing,

-   -   (a) the organic polymer (Z) and (b) a silane-based compound        substituted with amino group (B7).

(8)′ A sealant, a potting agent, a coating material or an adhesive,characterized in that it is composed of a curable composition,containing,

the organic polymer (Z), a filler (F), a plasticizer (G),a curingcatalyst (H) and an organocarboxylate compound (B8).

(9)′ A sealant, a potting agent, a coating material or an adhesive,characterized in that it is composed of a curable rubber composition,containing,

-   -   the organic polymer (Z),    -   alcohols (B9), and/or a hydrolyzable ester compound (I) (except        the hydrolyzable organosilicon compound (B10) and    -   a hydrolyzable organosilicon compound (B10).

(10)′ A sealant, a potting agent, a coating material or an adhesive,characterized in that it is composed of a two- or multi-liquid typecrosslinkable rubber composition composed of at least two liquids,characterized in that it contains,

-   -   the major ingredient (I) containing the organic polymer (Z), a        curing agent (II) containing    -   a silanol condensing catalyst (J) and water or a hydrate of a        metallic salt (B11).

The compositions of the present invention are also used for a sealant, apotting agent, a coating material or an adhesive, characterized in thatit is composed of a crosslinkable rubber composition comprising theorganic polymer (Z1), a high-molecular compound (K) other than thepolymer (Z1) and/or an inorganic filler (L). More concretely, thesecompositions include the followings.

(11)′ A sealant, a potting agent, a coating material or an adhesive,characterized in that it is composed of a crosslinkable rubbercomposition, containing the organic polymer (Z1) and an organosiliconpolymer (K1).

(12)′ A sealant, a potting agent, a coating material or an adhesive,characterized in that it is composed of a crosslinkable rubbercomposition, containing the organic polymer (Z1), organic rubber (K2)and a crosslinking agent (M) for the organic rubber (K2).

(13)′ A sealant, a potting agent, a coating material or an adhesive,characterized in that it is composed of a crosslinkable rubbercomposition, containing the organic polymer (Z1), an epoxy resin (K3), asilane coupling agent (N), a silanol condensing catalyst (O) and acuring agent (P) for the epoxy resin.

(14)′ A sealant, a potting agent, a coating material or an adhesive,characterized in that it is composed of a crosslinkable rubbercomposition, containing the organic polymer (Z1), an epoxy resin (K3), asilicon compound (Q) containing a functional group reactive with theepoxy group and hydrolyzable silyl group in the molecule and a siliconcompound (R) containing at least two hydroxyl groups bonded to thesilicon atom in the molecule.

(15)′ A sealant, a potting agent, a coating material or an adhesive,characterized in that it is composed of a crosslinkable rubbercomposition, containing the organic polymer (Z1), calcium carbonate (L1)and talc (L2).

(16)′ A sealant, a potting agent, a coating material or an adhesive,characterized in that it is composed of a curable composition,containing (a) the organic polymer (Z), (b) a nickel-containing lightstabilizer (S) and (C) a silane coupling agent (T).

(17)′ A sealant, a potting agent, a coating material or an adhesive,characterized in that it is composed of a crosslinkable rubbercomposition, containing the organic polymer (Z) and a sulfur-based aginginhibitor (U).

(18)′ A sealant, a potting agent, a coating material or an adhesive,characterized in that it is composed of a curable composition,containing the organic polymer (Z), and a compound (V) having, in themolecule, an unsaturated group capable of triggering polymerization byreacting with oxygen in air and/or a photopolymerizable material.

(20)′ A sealant, a potting agent, a coating material or an adhesive,characterized in that it is composed of a crosslinkable rubbercomposition, containing

-   -   the organic polymer (Z) and    -   a curing catalyst (H) composed of a mercaptide type organotin        compound (H3) having the Sn—S bond, a sulfide type organotin        compound (H4) having the Sn═S bond, organocarboxylic acid (H5),        organocarboxylic anhydride (H6), or a mixture of one of the        above compounds and a carboxylic type organotin compound (H7).

(21)′ A sealant, a potting agent, a coating material or an adhesive,characterized in that it is composed of a curable composition,containing

-   -   the organic polymer (Z) and    -   a compound (H8) as the curing catalyst (H), represented by the        general formula Q₂Sn(OZ)₂ or [Q₂Sn(OZ)]₂O,    -   wherein, Q is a monovalent hydrocarbon group of 1 to 20 carbon        atoms; and Z is a monovalent hydrocarbon group of 1 to 20 carbon        atoms or organic group having functional group capable of        forming therein a coordination bond with Sn.

(22)′ A sealant, a potting agent, a coating material or an adhesive,characterized in that it is composed of a curable rubber composition,containing the organic polymer (Z) and titanates (Y).

(23)′ A coating material for vehicles, characterized in that it containsthe silyl-containing

-   -   ethylene/α-olefin/non-conjugated polyene random copolymer rubber        (A1).

(24)′ A sealant, a potting agent, a coating material for purposes otherthan vehicles or an adhesive, characterized in that it is composed of acurable composition, containing the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1).

(25)′ A sealant for laminated glass, characterized in that it contains

-   -   the silyl-containing ethylene/α-olefin/non-conjugated polyene        random copolymer rubber (A2), a curing catalyst (H) and water or        a hydrate of a metallic salt (B11).

(26)′ A sealant for laminated glass, characterized in that it contains

-   -   the silyl-containing ethylene/α-olefin/non-conjugated polyene        random copolymer rubber (A2), a hot melt resin (X), a curing        catalyst (H) and water or a hydrate of a metallic salt (B11).

The silyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A2) normally contains at least one type ofsilyl-containing unit represented by the general formula (2) or (3).

It is particularly preferable that the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A2) isproduced by reacting an ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber having a norbornene compound as the non-conjugatedpolyene with at least one terminal vinyl group represented by thegeneral formula (4) and/or (5), with a silicon compound represented bythe general formula (6), to add SiH group of the silicon compound to thedouble bond of the copolymer rubber.

In the sealant, the potting agent, the coating material or the adhesive(23)′ to (26)′, the silyl-containing ethylene/α-olefin/non-conjugatedpolyene random copolymer rubber (A2) may be also used in place of thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1), and vice versa.

BEST MODES FOR CARRYING OUT THE INVENTION

The curable compositions and their uses of the present invention aredescribed more concretely.

Curable Elastomer Composition (1)

The curable elastomer composition (1) of the present invention comprisesa silyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1) and a compound having a silanol group and/or acompound which can react with moisture to form a compound having asilanol group in the molecule (B1)

[Silyl-Containing ethylene/α-olefin/Non-Conjugated polyene Randomcopolymer Rubber (A1)]

The silyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1) for the present invention contains a hydrolyzablesilyl group, represented by the following general formula [III], and canbe produced by, e.g., reacting a specificethylene/α-olefin/non-conjugated polyene random copolymer rubber (A₀)with a specific silicon compound (hydrosilylation reaction):

R in the general formula [III] is a monovalent hydrocarbon group of 1 to12 carbon atoms which may be substituted or not, preferably a monovalenthydrocarbon group free of aliphatic unsaturated bond, including alkyl,e.g., methyl, ethyl, propyl, butyl, hexyl or cyclohexyl; aryl, e.g.,phenyl or tolyl; or the above-described group whose hydrogen atom bondedto the carbon atom is totally or partly substituted with a halogen,e.g., fluorine.

X is a hydrolyzable group selected from the group consisting of hydride(—H), halogen, alkoxyl, acyloxy, ketoxymate, amide, acidamide, aminoxy,mercapto, alkenyloxy, thioalkoxy and amino group.

The concrete examples of halogen, alkoxyl, acyloxy, ketoxymate, acidamide and thioalkoxy group are those for X in the general formula [IV],described later.

“a” is an integer of 0 to 2, preferably 0 or 1.

Ethylene/α-Olefin/Non-Conjugated Polyene Random Copolymer Rubber (A₀)

The ethylene/α-olefin/non-conjugated polyene random copolymer rubber(A₀) for the present invention is a random copolymer of ethylene,α-olefin of 3 to 20 carbon atoms, and non-conjugated polyene.

The concrete examples of the α-olefins of 3 to 20 carbon atoms includepropylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene,1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene,1-pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicosene,9-methyl-l-decene, 11-methyl-1-dodecene, and 12-ethyl-l-tetradecene.

Of these, the α-olefins of 3 to 10 carbon atoms are more preferable, inparticular propylene, 1-butene, 1-hexene and 1-octene.

These α-olefins may be used either individually or in combination.

The non-conjugated polyene for the present invention is a norbornenecompound with a vinyl group at the terminal, represented by thefollowing general formula [I] or [II]:

-   -   “n” is an integer of 0 to 10,    -   R¹ is hydrogen atom or    -   an alkyl group of 1 to 10 carbon atoms, e.g., methyl, ethyl,        propyl, isopropyl, n-butyl, i-butyl, sec-butyl, t-butyl,        n-pentyl, i-pentyl, t-pentyl, neopentyl, hexyl, i-hexyl, heptyl,        octyl, nonyl, and decyl,    -   R² is hydrogen atom or    -   an alkyl group of 1 to 5 carbon atoms of the concrete examples        for R¹,

wherein, R³ is hydrogen atom

or an alkyl group of 1 to 10 carbon atoms, the concrete example of whichis the same as the example for R¹.

The specific examples of the norbornene compounds represented by thegeneral formula [I] or [II] include 5-methylene-2-norbornene,5-vinyl-2-norbornene, 5-(2-propenyl)-2-norbornene,5-(3-butenyl)-2-norbornene, 5-(1-methyl-2-propenyl)-2-norbornene,5-(4-pentenyl)-2-norbornene, 5-(1-methyl-3-butenyl)-2-norbornene,5-(5-hexenyl)-2-norbornene, 5-(1-methyl-4-pentenyl)-2-norbornene,5-(2,3-dimethyl-3-butenyl)-2-norbornene,5-(2-ethyl-3-butenyl)-2-norbornene, 5-(6-heptenyl)-2-norbornene,5-(3-methyl-5-hexenyl)-2-norbornene,5-(3,4-dimethyl-4-pentenyl)-2-norbornene,5-(3-ethyl-4-pentenyl)-2-norbornene, 5-(7-octenyl)-2-norbornene,5-(2-methyl-6-heptenyl)-2-norbornene,5-(1,2-dimethyl-5-hexenyl)-2-norbornene,5-(5-ethyl-5-hexenyl)-2-norbornene, and5-(1,2,3-trimethyl-4-pentenyl)-2-norbornene. Of these, more preferableones are 5-vinyl-2-norbornene, 5-methylene-2-norbornene,5-(2-propenyl)-2-norbornene, 5-(3-butenyl)-2-norbornene,5-(4-pentenyl)-2-norbornene, 5-(5-hexenyl)-2-norbornene,5-(6-heptenyl)-2-norbornene and 5-(7-octenyl)-2-norbornene. Thenorbornene compounds may be used either individually or in combination.

A non-conjugated polyene shown below may be used, in addition to theabove-described one, e.g., 5-vinyl-2-norbornene, within limits notdetrimental to the object of the present invention.

More concretely, these non-conjugated polyenes include linearnon-conjugated polyenes, e.g., 1,4-hexadiene, 3-methyl-1,4-hexadiene,4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene,4,5-dimethyl-1,4-hexadiene, 7-methyl-1,6-octadiene; cyclicnon-conjugated polyenes, e.g., methyltetrahydroindene,5-ethylidene-2-norbornene, 5-methylene-2-norbornene,5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene,6-chloromethyl-5-isopropenyl-2-norbornene and dicyclopentadiene; andtrienes, e.g., 2,3-diisopropylidene-5-norbornene,2-ethylidene-3-isopropylidene-5-norbornene and2-propenyl-2,2-norbornadiene.

The ethylene/α-olefin/non-conjugated polyene random copolymer rubber(A₀) comprising the above components has the following properties.

(i) Molar Ratio of ethylene to α-Olefin of 3 to 20 Carbon Atoms(ethylene/α-Olefin)

The ethylene/α-olefin/non-conjugated polyene random copolymer rubber(A₀) contains (a) the unit derived from

-   -   ethylene and (b) the unit derived from α-olefin of 3 to 20        carbon atoms (sometimes referred simply as “α-olefin”        hereinafter) in a molar ratio of 40/60 to 95/5, preferably 50/50        to 90/10, more preferably 55/45 to 85/15, still more preferably        60/40 to 80/20 [(a)/(b) molar ratio].

The random copolymer rubber can give, when its (a)/(b) molar ratio fallsin the above range, a rubber composition which is formed into acrosslinked rubber shape excellent in resistance to aging under heating,strength characteristics and rubber elasticity, and, at the same time,excellent in resistance to cold temperature and moldability.

(ii) Iodine Value

The ethylene/α-olefin/non-conjugated polyene random copolymer rubber(A₀) has an iodine value of 0.5 to 50 (g/100 g), preferably 0.8 to 40(g/100 g), more preferably 1 to 30 (g/100 g), still more preferably 1.5to 25 (g/100 g).

The random copolymer rubber can give, when its iodine value falls in theabove range, a desired content of the hydrolyzable silyl group, and arubber composition which is formed into a crosslinked rubber shapeexcellent in compression-resistant permanent set and resistant to agingunder service conditions (under heating) An iodine value exceeding 50 isdisadvantageous costwise and hence undesirable.

(iii) Intrinsic Viscosity

The ethylene/α-olefin/non-conjugated polyene random copolymer rubber(A₀) has an intrinsic viscosity [η] of 0.001 to 2 dl/g, determined indecalin kept at 135° C., preferably 0.01 to 2 dl/g, more preferably 0.05to 1.0 dl/g, still more preferably 0.05 to 0.7 dl/g, still morepreferably 0.1 to 0.5 dl/g.

The random copolymer rubber can give, when its intrinsic viscosity [η]falls in the above range, a highly fluidic rubber composition which isformed into a crosslinked rubber shape excellent in strength propertiesand compression-resistant permanent set.

(iv) Molecular Weight Distribution (Mw/Mn)

The ethylene/α-olefin/non-conjugated polyene random copolymer rubber(A₀) has a molecular weight distribution (Mw/Mn) of 3 to 100, determinedby gel permeation chromatography (GPC), preferably 3.3 to 75, morepreferably 3.5 to 50.

The random copolymer rubber can give, when its molecular weightdistribution (Mw/Mn) falls in the above range, a rubber compositionwhich is formed into a crosslinked rubber shape excellent infabricability and strength properties.

The ethylene/α-olefin/non-conjugated polyene random copolymer rubber(A₀) is produced by the random copolymerization with ethylene, anα-olefin of 3 to 20 carbon atoms and a norbornene compound with a vinylgroup at the terminal, represented by the general formula [I] or [II]under the conditions of a polymerization temperature: 30 to 60° C.(preferably 30 to 59° C.), a polymerization pressure: 4 to 12 kgf/cm²(preferably 5 to 8 kgf/cm²), and a molar ratio of charged non-conjugatedpolyene to ethylene (non-conjugated polyene/ethylene): 0.01 to 0.2, inthe presence of a catalyst which contains the compounds (h) and (i)described below as the major ingredients. The random copolymerization ispreferably effected in a hydrocarbon solvent.

(h) A soluble vanadium compound represented by the general formulaVO(OR)_(n)X_(3-n) (wherein, R is a hydrocarbon group; X is a halogenatom; and “n” is an integer of 0 to 3) or a vanadium compoundrepresented by VX₄ (wherein, X is a halogen atom)

The above-described soluble vanadium compound (h) is the componentsoluble in the hydrocarbon solvent for the polymerization system. Moreconcretely, the representative ones are vanadium compounds representedby the general formula VO(OR)_(a)X_(b) or V(OR)_(c)X_(d) (wherein, R isa hydrocarbon group, 0≦a≦3, 0≦b≦3, 2≦a+b≦3, 0≦c≦4, 0≦d≦4, and 3≦c+d≦4),and adducts of the electron donors for these compounds.

Still more concretely, the examples of these compounds include VOCl₃,VO(OC₂H₅)Cl₂, VO(OC₂H₅)₂Cl, VO(O-iso-C₃H₇)Cl₂, VO(O-n-C₄H₉)Cl₂,VO(OC₂H₅)₃, VOBr₃, VCl₄, VOCl₃, VO(O-n-C₄H₉)₃ and VCl₃.2OC₆H₁₂OH.

(i) An organoaluminum compound represented by the general formulaR′_(m)AlX′_(3-m) (wherein, R′ is a hydrocarbon group; X is a halogenatom; and “m” is an integer of 1 to 3).

The concrete examples of the organoaluminum compounds (i) include

-   -   trialkyl aluminum, e.g., triethyl aluminum, tributyl aluminum        and triisopropyl aluminum;    -   dialkyl aluminum alkoxide, e.g., diethyl aluminum ethoxide and        dibutyl aluminum butoxide;    -   alkyl aluminum sesquialkoxide, e.g., ethyl aluminum        sesquiethoxide and butyl aluminum sesquibutoxide;    -   partially alkoxylated alkyl aluminum, having an average        composition represented by the general formula R¹        _(0.5)Al(OR¹)_(0.5) or the like;    -   dialkyl aluminum halide, e.g., diethyl aluminum chloride,        dibutyl aluminum chloride and diethyl aluminum bromide;    -   partially halogenated alkyl aluminum, e.g., alkyl aluminum        sesquihalide (e.g., ethyl aluminum sesquichloride, butyl        aluminum sesquichloride and ethyl aluminum sesquibromide), and        alkyl aluminum dihalide (e.g., ethyl aluminum dichloride, propyl        aluminum dichloride and butyl aluminum dibromide);    -   partially hydrogenated alkyl aluminum, e.g., dialkyl aluminum        hydride (e.g., diethyl aluminum hydride and dibutyl aluminum        hydride), and alkyl aluminum dihydride (e.g., ethyl aluminum        dihydride and propyl aluminum dihydride); and    -   partially alkoxylated or halogenated alkyl aluminum, e.g., ethyl        aluminum ethoxychloride, butyl aluminum butoxychloride and ethyl        aluminum ethoxybromide.

It is preferable to use the catalyst comprising the soluble vanadiumcompound represented by VOCl₃ as a compound (h) and a blend ofAl(OC₂H₅)₂Cl/Al₂(OC₂H₅)₃Cl₃ (blending ratio: 1/5 or more) as compounds(i), because it gives an

ethylene/α-olefin/non-conjugated polyene random copolymer rubber (A₀)containing the insolubles at 1% or less, after it is treated with aSoxhlet extractor (solvent: boiling xylene, extraction time: 3 hours,and mesh: 325).

A metallocene catalyst, e.g., that disclosed by Japanese PatentLaid-Open Publication No. 40586/1997, maybe used for thecopolymerization.

Silicon Compound

The silicon compound useful for the present invention is represented bythe following general formula [IV]:

R in the general formula [IV] is a monovalent hydrocarbon group of 1 to12 carbon atoms, which may be substituted or not, preferably free of anunsaturated aliphatic bond, including alkyl, e.g., methyl, ethyl,propyl, butyl, hexyl and cyclohexyl; aryl, e.g., phenyl and tolyl; andthese groups whose hydrogen atoms bonded to carbon atom are partially ortotally substituted with a halogen atom, e.g., fluorine.

X is a hydride (—H), halogen, alkoxyl, acyloxy, ketoxymate, amide, acidamide, aminoxy, mercapto, alkenyloxy, thioalkoxy, or amino group.

The halogen groups includes chlorine, fluorine, bromine and iodineatoms.

The alkoxyl groups include methoxy, ethoxy, propoxy,propoxybutoxy,isopropoxy,isobutoxy,sec-butoxy,tert-butoxy, pentyloxy,hexyloxy and phenoxy.

The acyloxy groups include acetoxy and beozoyloxy.

The ketoxymate groups include acetoxymate, dimethylketoxymate,diethylketoxymate and cyclohexylmate.

The amide groups include dimethylamide, diethylamide, dipropylamide,dibutylamide and diphenylamide.

The acid amide groups include carboxylic acid amide, maleic acid amide,acrylic acid amide and itaconic acid amide.

Thioalkoxy groups include thiomethoxy, thioethoxy, thiopropoxy,thioisopropoxy, thioisobutoxy, sec-thiobutoxy, tert-thiobutoxy,thiopentyloxy, thiohexyloxy and thiophenoxy.

The amino groups include dimethylamino, diethylamino, dipropylamino,dibutylamino and diphenylamino.

Of these groups, the alkoxyl groups, in particular those of 1 to 4carbon atoms, are more preferable.

“a” in the general formula [IV] is an integer of 0 to 2, preferably 0 or1.

The concrete examples of the silicon compounds represented by thegeneral formula [IV] include

-   -   halogenated silanes, e.g., trichlorosilane,        methyldichlorosilane, dimethylchlorosilane, ethyldichlorosilane,        diethylchlorosilane, phenyldichlorosilane and        diphenylchlorosilane;    -   alkoxysilanes, e.g., trimethoxysilane, triethoxysilane,        methyldimethoxysilane, ethyldimethoxysilane,        butyldimethoxysilane, methyldiethoxysilane, ethyldiethoxysilane,        butylethoxysilane and phenyldimethoxysilane;    -   acyloxysilanes, e.g., triacetoxysilane, methyldiacetoxysilane        and phenyldiacetoxysilane;    -   ketoxymatesilanes, e.g., tris(acetoxymate)silane,        bis(dimethylketoxymate)methylsilane,        bis(methylethylketoxymate)methylsilane,        bis(cyclohexylketoxymate)methylsilane;    -   aminoxysilanes, e.g., aminoxysilane and triaminoxysilane; and    -   aminosilanes, e.g., methyldiaminosilane and triaminosilane. Of        these compounds, alkoxysilanes are particularly preferable.

The silicon compound represented by the general formula [IV] ispreferably incorporated at 0.01 to 5 mols per mol of the double bondpresent in the ethylene/α-olefin/non-conjugated polyene random copolymerrubber (A₀), more preferably 0.05 to 3 mols.

The hydrosilylation reaction is effected in the presence of a transitionmetal complex catalyst.

The effective catalysts for the hydrosilylation reaction include acomplex compound of a Group VIII transition metal selected from thegroup consisting of platinum, rhodium, cobalt, palladium and nickel, ofwhich chloroplatinic acid and a platinum/olefin complex are particularlypreferable. In this case, the quantity of the catalyst is 0.1 to 10,000ppm as the metal unit based on the ethylene/α-olefin/non-conjugatedpolyene random copolymer rubber (A₀) as the reactant, preferably 1 to1000 ppm, more preferably 20 to 200 ppm.

The hydrosilylation reaction is effected at 30 to 180° C., preferably 60to 150° C., under an elevated pressure, as required, for around 10seconds to 10 hours.

A solvent may be used, although not essential. When it is to be used, aninert solvent, e.g., an ether or hydrocarbon, is preferable.

In the present invention, the hydrosilylation reaction produces theethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1)having a hydrolyzable silyl group, represented by one of the followinggeneral formulae. It is the ethylene/α-olefin/non-conjugated polyenerandom copolymer rubber (A₀) which has the SiH group of the siliconcompound, represented by the general formula [IV], bonded to the doublebond.

It is possible to add a siloxane hydrogen-modified at one terminal,represented by the following general formula, to the copolymer rubber(A1), in addition to the compound with a hydrolyzable silyl group,represented by the general formula [IV], to impart the weatherresistance, slippage and gas permeation characteristic of the siloxaneto the copolymer rubber:

wherein, R¹ is a monovalent hydrocarbon group of 1 to 12 carbon atoms,which may be substituted or not, like R for the general formula [IV],particularly preferably an alkyl group; and “m” is an integer of 5 to200, particularly preferably 10 to 150.Compound Having a Silanol Group and/or Compound Which Can React WithMoisture to Form a Compound Having a Silanol Group in the Molecule (B1)

The compound having a silanol group in the molecule for the presentinvention is not limited, so long as it has one ≡SiOH group in themolecule. The concrete examples of these compounds useful for thepresent invention include:

-   -   compounds represented by the general formula R₃SiOH (wherein, R        is an alkyl or aryl group, which may be substituted or not, and        may be the same or different), e.g., (CH₃)₃SiOH, (CH₃CH₂)₃SiOH,        (CH₃CH₂CH₂)₃SiOH, (n-C₄H₉)₃SiOH, (sec-C₄H₉)₃SiOH, (t-C₄H₉)₃SiOH,        (C₅H₁₁)₃SiOH, (C₆H₁₃)₃SiOH, (C₆H₅)₃SiOH, (C₆H₅)₂Si(CH₃)(OH),        (C₆H₅)Si(CH₃)₂(OH), (C₆H₅)₂Si(C₂H₅)(OH), (C₆H₅)Si(C₂H₅)₂(OH),        (C₆H₅)—CH₂Si(C₂H₅)₂(OH),

-   -   and cyclic polysiloxane compounds having a silanol group,

-   -   linear polysiloxane compounds having a silanol group, e.g.,

-   -   compounds having a silanol group bonded to the terminal of a        polymer whose main chain comprises silicon and carbon, e.g.,

-   -   componds having a silanol group bonded to the polysilane's main        chain at the terminal, e.g.,

-   -   compounds having a silanol group bonded to the terminal of a        polymer whose main chain comprises silicon, carbon and oxygen,        e.g.,

The compound having ≡SiOH group at a higher content shows the highereffect at the same quantity. (CH₃)₃SiOH and (CH₃CH₂)₃SiOH are morepreferable from this respect, and (C₆H₅)₃SiOH, (C₆H₅)₂Si(CH₃)(OH) and(C₆H₅)Si(CH₃)₂ (OH) are more preferable for their handling easiness andstability in air.

The compounds which can react with moisture to form a compound having asilanol group in the molecule for the present invention include thefollowings, each of which is known as the silylation agent:(CH₃)₃Si—NH—Si(CH₃)₃,(CH₃)₃SiN(CH₃)₂,(CH₃)₃SiO—C(CH₃)(NSi(CH₃)₃),

(CH₃)₃Si—NH—CO—NH—Si(CH₃)₃,and

CF₃—SO₂—OSi(CH₃)₃. They can be suitably used for the present invention,and (CH₃)₃Si—NH—Si(CH₃)₃ is particularly preferable for high content of≡SiOH group in the hydrolyzable product.

The compound (B1) has the effects of improving tensile characteristics(i.e., decreasing modulus and increasing elongation) of the curedproduct, and also residual tackiness. The improved tensilecharacteristics is conceivably due to the following phenomenon: thesilicon compound or the silanol compound as the hydrolysis productthereof reacts with the hydrolyzable silyl group in the silyl-containing

-   -   ethylene/α-olefin/non-conjugated polyene random copolymer rubber        (A1) in such a way to cap the group, to decrease the number of        the crosslinking points of the copolymer rubber (A1) and, in        turn, increase the molecular weight between the crosslinking        points, with the result that the cured product of low modulus        and high elongation is produced. The phenomenon involved in        improvement of the residual tackiness is not well understood. It        is, however, considered that the increased molecular weight        between the crosslinking points is accompanied by the decrease        in number of the free molecular chains/branches that are not        involved in the crosslinking, to decrease the residual        tackiness.

Quantity of the compound (B1) to be incorporated varies depending on theexpected properties of the cured product. It is incorporated at a ratedetermined by the ratio of the silanol (≡SiOH) equivalents per mol ofthe hydrolyzable silyl group in the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1).The compound (B1) is incorporated normally at 0.1 to 0.9 equivalents ofthe silanol group per mol of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1),to give the cured product of low modulus and high elongation. It isnecessary, however, to leave the hydrolyzable silyl group uncappeddespite the presence of the compound (B1) at a rate of at least 0.1groups in the molecule. The compound (B1) may be incorporated at morethan 0.9 equivalent of the silanol group, which, however, is notrecommended from the economic consideration. The compositionincorporating the compound (B1) at 0.3 equivalents or more, preferably0.5 equivalents or more, may not be sufficiently cured and left uncured.Surprisingly, however, the thin layer portion on the uncured compositionsurface is sufficiently cured to be completely tackiness-free. In otherwords, the composition is semi-cured, sufficiently cured in the surfaceportion but left uncured inside. Such a composition can suitably finduse for sealants, e.g., the so-called mastic sealant.

The methods for incorporating the compound (B1) fall into 3 generalcategories. The first method merely adds the compound (B1) to thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1), wherein it is uniformly dispersed and dissolvedby carefully setting the conditions, e.g., temperature and stirringconditions, as required in consideration of the compound (B1)properties. In this case, the composition may not be necessarilytransparent completely, and can sufficiently achieve the objectives evenwhen it is not transparent, so long as the composition (B1) issufficiently dispersed therein. A dispersibility improver, e.g.,surfactant, may be used, as required.

The second method mixes a given quantity of the compound (B1) with thefinal product, when it is used. For example, when the composition isused as a two-liquid type sealant, the compound (B1) may be mixed as thethird component with the base and curing agent for the composition.

The third method reacts the compound (B1) beforehand with thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1) in the presence of a tin-based, titanateester-based, acid or basic catalyst, as required, or in the presence ofwater when the compound (B1) is a compound which can react with moistureto form a compound having a silanol group in the molecule, followed byevaporation under a vacuum and heating.

The concrete examples of the catalysts useful for the present inventioninclude:

-   -   titanate esters, e.g., those of tetrabutyl titanate and        tetrapropyl titanate;    -   organotin compounds, e.g., dibutyl tin dilaurate, dibutyl tin        maleate, dibutyl tin diacetate, tin octylate and tin        naphthenate; lead octylate;    -   amine-based compounds and salts of these compounds and        carboxylates, e.g., butylamine, octylamine, dibutylamine,        monoethanolamine, diethanolamine, triethanolamine,        diethylenetriamine, triethylenetetramine, oleylamine,        octylamine, cyclohexylamine, benzylamine,        diethylaminopropylamine, xylylenediamine, triethylenediamine,        guanidine, diphenylguanidine, 2,4,6-tris(dimethylaminomethyl)        phenol, morpholine, N-methyl morpholine, and        1,3-diazabicyclo(5,4,6) undecene-7 (DBU);    -   low-molecular-weight polyamide resins produced by the reactions        of excessive quantities of polyamines and polybasic acids;    -   products of the reactions between excessive quantities of        polyamines and epoxy compounds; and    -   silanol condensing catalysts, e.g., silane coupling agents        containing amino group (e.g., γ-aminopropyl trimethoxy silane        and N-(β-aminoethyl)aminopropyl methyldimethoxy silane). These        compounds may be used either individually or in combination.

The curable elastomer composition (1) of the present invention thusproduced may be incorporated, as required, with various additives, e.g.,white carbon, carbon black, calcium carbonate, titanium oxide, talc,asbestos and glass fibers, which serve, e.g., as a reinforcing ornon-reinforcing filler, a plasticizer, an antioxidant, an ultravioletray absorber, a pigment, or a flame retardant, so as to be useful as anadhesive, tackifier, paint and sealant compositions, waterproofmaterial, spray material, shaping material or casting rubber material.Of these, application to sealant and tackifiner agent compositions isespecially useful.

The curable elastomer composition (1) of the present invention, whenused as a sealant, may be incorporated, as required, with a plasticizer,a filler, a reinforcing agent, a dripping inhibitor, a colorant, anaging inhibitor, an adhesion promoter, a curing catalyst or a propertyadjuster.

The plasticizers useful for the present invention include:

-   -   phthalate esters, e.g., dibutylphthalate, diheptyl phthalate,        di(2-ethylhexyl) phthalate, butyl benzyl phthalate and bytyl        phthalyl butyl glycolate;    -   non-aromatic, dibasic acid esters, e.g., dioctyl adipate and        dioctyl cebacate;    -   esters of polyalkylene glycol, e.g., diethylene glycol        dibenzoate and triethylene glycol dibenzoate;    -   phosphate esters, e.g., tricresyl phosphate and tributyl        phosphate;    -   chlorinated paraffins; and    -   hydrocarbon-based oils, e.g., polybutene, hydrogenated        polybutene, ethylene/α-olefin oligomer, α-methyl styrene        oligomer, biphenyl, triphenyl, triaryl dimethane, alkylene        triphenyl, liquid polybutadiene, hydrogenated liquid        polybutadiene, alkyl diphenyl, partially hydrogenated        ter-phenyl, paraffin oil, naphthene oil and atactic        polypropylene. The above compound is selected, depending on        specific purposes, e.g., adjustment of characteristics and        properties. They may be used either individually or in        combination, although not necessarily essential.

Of these, the hydrocarbon-based compounds free of unsaturated group(e.g., hydrogenated polybutene, hydrogenated liquid polybutadiene,paraffin oil, naphthene oil and atactic polypropylene) are morepreferable, because they are well compatible with various components forthe composition of the present invention, affecting curing speed of therubber composition to only a limited extent, giving the cured product ofhigh resistance to weather, and inexpensive.

The above plasticizer may replace the solvent used when a hydrolyzablesilyl group is introduced in the ethylene/α-olefin/non-conjugatedpolyene random copolymer rubber (A₀), in order to adjust reactiontemperature and viscosity of the reaction system.

The fillers and reinforcing agents useful for the present inventioninclude limestone powder and calcium carbonate; calcium carbonatesurface-treated with a fatty acid, resin acid, or cationic or anionicsurfactant; magnesium carbonate; talc; titanium oxide; barium sulfate;alumina; powder of metal (e.g., aluminum, zinc or iron); bentonite;kaolin clay; fumed silica; quartz powder; and carbon black. These arethe common ones, and one or more of these compounds may be used. Ofthese, the filler or reinforcing agent capable of impartingtransparency, e.g., fumed silica, can give the sealant with hightransparency.

The dripping inhibitors useful for the present invention include ahydrogenated castor oil derivative; and metallic soaps, e.g., calciumstearate, aluminum stearate and barium stearate. A dripping inhibitormay not be necessary, depending on purposes of the curable composition,and a filler or reinforcing agent incorporated.

The colorants useful for the present invention include the commoninorganic and organic pigments, and dyes, each of which may be used, asrequired.

The property adjusters useful for the present invention include varioussilane coupling agents: such as alkyl alkoxy silanes, e.g.,methyltrimethoxy silane, dimethyldimethoxy silane, trimethylmethoxysilane and n-propyltrimethoxy silane; alkyl isopropenoxy silanes, e.g.,dimethyldiisopropenoxy silane, methyltriisopropenoxy silane andγ-glycidoxypropylmethyldiisopropenoxy silane; alkoxy silanes having afunctional group, e.g., γ-glycidoxypropylmethyldimethoxy silane,γ-glycidoxypropyltrimethoxy silane, vinyl trimethoxy silane,vinyldimethylmethoxysilane, γ-aminopropyltrimethoxysilane,N-(β-aminoethyl)aminopropylmethyldimethoxy silane,γ-mercaptopropyltrimethoxy silane and γ-mercaptopropylmethyldimethoxysilane; silicone varnishes; and polysiloxanes.

The above property adjuster can increase hardness, or decrease hardnessand increase elongation of the curable elastomer composition (1) of thepresent invention, when it is cured.

Use of an adhesion promoter is not essential, because thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1) per se is adhesive to glass, other ceramicmaterials and metals, and adhesive to materials in a wider range in thepresence of a primer of every kind. However, the composition can improveadhesion to materials in a still wider range, when incorporated with oneor more types of epoxy resin, phenolic resin, varying silane couplingagents, alkyl titanates or aromatic polyisocyanates.

The curing catalysts useful for the present invention include: titanateesters, e.g., those of tetrabutyl titanate and tetrapropyl titanate;organotin compounds, e.g., dibutyl tin dilaurate, dibutyl tin maleate,dibutyl tin diacetate, tin octylate and tin naphthenate; lead octylate;amine-based compounds and salts of these compounds and carboxylates,e.g., butylamine, octylamine, dibutylamine, monoethanolamine,diethanolamine, triethanolamine, diethylenetriamine,triethylenetetramine, oleylamine, octylamine, cyclohexylamine,benzylamine, diethylaminopropylamine, xylylenediamine,triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris(dimethylaminomethyl) phenol, morpholine, N-methyl morpholine, and1,3-diazabicyclo(5,4,6) undecene-7 (DBU); low-molecular-weight polyamideresin products of the reactions between excessive quantities ofpolyamines and polybasic acids; products of the reactions betweenexcessive quantities of polyamines and epoxy compounds; and knownsilanol condensing catalysts, e.g., silane coupling agents containingamino group (e.g., γ-aminopropyl trimethoxy silane andN-(β-aminoethyl)aminopropyl methyldimethoxy silane). These compounds maybe used either individually or in combination. The curing catalyst maybe dissolved in a solvent for, e.g., improving workability and reducingviscosity. The solvent useful for the above purposes include aromatichydrocarbon-based ones, e.g., toluene and xylene; ester-based ones,e.g., ethyl acetate, butyl acetate, amyl acetate and cellosolve acetate;and ketone-based ones, e.g., methylethylketone, methylisobutylketone anddiisobutylketone. The solvent may be used during the process ofproducing the silyl-containing ethylene/α-olefin/non-conjugated polyenerandom copolymer rubber (A1).

The aging inhibitors useful for the present invention include a commonantioxidant, e.g., a sulfur-based one, radical inhibitor and ultravioletray absorber, although use of the aging inhibitor is not essential.

The sulfur-based aging inhibitors useful for the present inventioninclude mercaptans, salts thereof, sulfides including sulfidecarboxylate esters and hindered phenol-based sulfides, polysulfides,dithiocarboxylates, thioureas, thiophosphates, sulfonium compounds,thioaldehydes, thioketones, mercaptals, mercaptols, monothio acids,polythio acids, thioamides, and sulfoxides.

More concretely, the sulfur-based aging inhibitors include:

-   -   mercaptans, e.g., 2-mercaptobenzothiazole; salts of mercaptans,        e.g., zinc salt of 2-mercaptobenzothiazole;    -   sulfides, e.g., 4,4′-thio-bis(3-methyl-6-t-butyl phenol),        4,4′-thio-bis(2-methyl-6-t-butyl phenol),        2,2′-thio-bis(4-methyl-6-t-butyl phenol),        bis(3-methyl-4-hydroxy-5-t-butylbenzyl) sulfide, terephthaloyl        di(2,6-di-methyl-4-t-butyl-3-hydroxybenzyl) sulfide,        phenothiazine, 2,2′-thio-bis-(4-octylphenol) nickel, dilauryl        thiodipropionate, distearyl thiodipropionate, dimyristyl        thiodipropionate, ditridecyl thiodipropionate,        distearylβ,β′-thiodibutyrate, lauryl-stearylthiodipropionate and        2,2-thio[diethyl-bis-3(3,5-di-t-butyl-4-hydroxy        phenol)propionate];    -   polysulfides, e.g., 2-benzothiazole disulfide;    -   dithiocarboxylates, e.g., zinc dibutyldithiocarbamate, zinc        diethyldithiocarbamate, nickel dibutyldithiocarbamate, zinc        di-n-butyldithiocarbamate, dibutyl ammonium        dibutyldithiocarbamate, zinc ethyl-phenyl-dithiocarbamate and        zinc dimethylcarbamate;    -   thioureas, e.g., 1-butyl-3-oxy-diethylene-2-thiourea,        di-o-tolyl-thiourea and ethylene thiourea; and    -   thiophosphates, e.g., trilauryltrithiophosphate.

The above-described sulfur-based aging inhibitor preventsdecomposition/aging of the main chain under heating much moreefficiently than the other types for the curable rubber composition ofthe present invention, controlling the problems, e.g., residual surfacetackiness.

The radical inhibitors useful for the present invention includephenol-based ones, e.g., 2,2-methylene-bis(4-methyl-6-t-butyl phenol)and tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propio nate]methane; and amine-based ones, e.g., phenyl-β-naphthylamine,α-naphthylamine and N,N′-sec-butyl-p-phenylenediamine, phenothiazine andN,N′-diphenyl-p-phenylenediamine.

The ultraviolet ray absorbers useful for the present invention include2-(2′-hydroxy-3′,5′-di-t-butylphenyl) benzotriazole andbis(2,2,6,6-tetramethyl-4-piperidine) cebacate.

The aging inhibitor is incorporated at about 0.1 to 20 parts by weightper 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1),preferably 1 to 10 parts by weight.

The sealant composition maybe prepared for a one-liquid type, where thecomposition of all of the components is prepared beforehand and sealed,and cured with moisture in air after it is applied, or for a two-liquidtype, where the separately prepared curing agent composition of, e.g., acuring catalyst, a filler, a plasticizer and water as the curing agentis mixed with the silyl-containing ethylene/α-olefin/non-conjugatedpolyene random copolymer rubber before use.

When the sealant composition is used for the one-liquid type, it ispreferable that the water-containing component is dehydrated/driedbeforehand, or dehydrated during mixing/kneading under a vacuum, becauseit contains all of the components before use.

When used for the two-liquid type, on the other hand, the sealantcomposition may contain water to some extent, because thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1) is not incorporated beforehand with the curingcatalyst and hence will not be gelled even in the presence of water.Nevertheless, however, it is preferable to dehydrate/dry thecomposition, when it is required to have storage stability for extendedperiods.

The preferable dehydration/drying method is drying under heating for thesolid, e.g., powdery, composition, and dehydration under a vacuum or inthe presence of synthetic zeolite, activated alumina or silica gel forthe liquid composition. Moreover, it maybe dehydrated in the presence ofa small quantity of an isocyanate compound, where the isocyanate groupreacts with water. The composition will have still improved storagestability, when treated for the above-mentioned dehydration/drying andincorporated with a lower alcohol, e.g., methanol or ethanol; oralkoxysilane compound, e.g., n-propyltrimethoxy silane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane andγ-glycidoxypropyltrimethoxysilane.

The curable elastomer composition (1) of the present invention, whenused as a tackifier, may be incorporated, as required, with a curingcatalyst, an aging inhibitor, a plasticizer, a reinforcing agent, aproperty adjuster or a solvent, which can be used for the sealant. Itmay be further incorporated, depending on its purposes, a known additivecommonly used for tackifiers, e.g., rosin ester resin, phenol resin,xylene resin, xylene/phenol resin, coumarone resin, petroleum-basedresin (e.g., aromatic-, aliphatic/aromatic copolymer- or alicyclic-basedresin), terpene resin, terpene/phenol resin or low-molecular-weightpolystyrene resin. The tackifier composition can find wide uses, e.g.,tapes, sheets, labels and foils. For example, the above-describedtackifier composition, of non-solvent liquid, solvent type, emulsiontype or hot-melt type, is applied to a base material, e.g., syntheticresin or modified natural film, paper, any type of cloth, metallic foil,metallized plastic foil, asbestos or cloth of glass fibers, and cured atnormal or elevated temperature after being exposed to moisture or water.

Curable Elastomer Composition (1) and its Uses

The curable elastomer composition (1) of the present invention containsthe curable composition with the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber as thecomponent (A1), as described in detail earlier. More concretely, itcontains the organic polymer (Z) containing the hydrolyzable silyl grouprepresented by the general formula [III] and essentially no unsaturateddouble bond in the main chain, and the compound (B1) having a silanolgroup and/or the compound which can react with moisture to form acompound having a silanol group in the molecule.

It can be suitably used for electric/electronic device members,transportation machines, and civil engineering/construction, medical andleisure areas, as described in DISCLOSURE OF THE INVENTION.

The curable elastomer composition (1) of the present invention can beused as a sealant, a potting agent, a coating material or an adhesivefor electric/electronic device members, transportation machines, andcivil engineering/construction, medical and leisure areas.

The curable elastomer composition (1) of the present invention isdeveloped by the inventors of the present invention, who haveextensively studied a composition which can replace the propyleneoxide-based polymer described in BACKGROUND OF THE INVENTION, and givethe cured product improved in elongation and residual surface tackiness,faster in curing speed and higher in resistance to weather. They havefound that the composition containing a silyl-containing

-   -   ethylene/α-olefin/non-conjugated polyene random copolymer rubber        having a structural unit derived from a norbornene compound as        the non-conjugated polyene with a specific terminal vinyl group,        and containing a specific hydrolyzable silyl group in the        molecule and a compound having a silanol group and/or a compound        which can react with moisture to form a compound having a        silanol group in the molecule is faster in curing speed, can        give the cured product of higher resistance to weather, improved        in elongation and residual surface tackiness, reaching the        present invention.

Japanese Patent Laid-Open Publication Nos. 34066/1986 and 34067/1986,cited earlier, are completely silent on anethylene/α-olefin/non-conjugated polyene random copolymer rubber havinga structural unit derived from a norbornene compound with a specificterminal vinyl group, and containing a specific hydrolyzable silyl groupin the molecule.

Curable Rubber Composition (2)

The curable rubber composition (2) of the present invention is composedof the silyl-containing

-   -   ethylene/α-olefin/non-conjugated polyene random copolymer rubber        (A1), a tetravalent tin compound (C), a silicon compound (B2)        and, as required, a silane coupling agent containing isocyanate        group.

Tetravalent Tin Compound (C)

The curable rubber composition (2) of the present invention contains atetravalent tin compound (C) as the high-activity, silanol condensingcatalyst.

More concretely, the tetravalent tin compounds (C) useful for thepresent invention include:

-   -   tin carboxylates,    -   dialkyl tin oxides, and    -   tin compounds represented by the general formula        Q_(d)Sn(OZ)_(4-d) or [Q₂Sn(OZ)]₂O (wherein, Q is a monovalent        hydrocarbon group of 1 to 20 carbon atoms; Z is a monovalent        hydrocarbon group of 1 to 20 carbon atoms or an organic group        having a functional group which can form a coordinate bond with        Sn within its structure; and “d” is an integer of 1 to 3).

The other effective curing catalyst significantly accelerating thesilanol condensation is the product by the reactions between atetravalent tin compound (e.g., dialkyl tin oxide or dialkyl tindiacetate) and low-molecular-weight silicon compound having ahydrolyzable silicon group (e.g., tetraethoxy silane, methyltriethoxysilane, diphenyl dimethoxy silane or phenyl trimethoxy silane).

Of these, the tin compounds represented by the above-described generalformula (i.e., chelate compounds, e.g., dibutyl tin bisacetylacetate, ortin alcolates) are more preferable, because they have high activity asthe silanol condensing catalysts, and accelerate curing of the rubbercomposition. The tin alcolates are still more preferable, because theyaccelerate curing of the curable rubber composition of the presentinvention more notably, and have longer workable time, i.e., time spanfor which works, e.g., spatula finishing, can be done after the mainingredient is kneaded with the curing agent.

The tin carboxylates useful for the present invention include: dibutyltin dilaurate, dibutyl tin diacetate, dibutyl tin diethylhexanolate,dibutyl tin dioctate, dibutyl tin dimethylmaleate, dibutyl tindiethylmaleate, dibutyl tin dibutylmaleate, dibutyl tindiisooctylmaleate, dibutyl tin ditridecylmaleate, dibutyl tindibenzylmaleate, dibutyl tin maleate, dioctyltindiacetate,dioctyltindistearate, dioctyl tin dilaurate, dioctyl tin diethylmaleateand dioctyl tin diisooctylmaleate.

The dialkyl tin oxides useful for the present invention include: dibutyltin oxide, dioctyl tin oxide, and a mixture of dibutyl tin oxide and aphthalate ester.

The concrete examples of the chelate compounds include:

The concrete examples of the tin alcolates include:(C₄H₉)₃SnOCH₃,(C₄H₉)₂Sn (OCH₃)₂,C₄H₉Sn (OCH₃)₃,Sn(OCH₃)₄,(C₄H₉)₂Sn(OC₃H₇)₂,(C₄H₉)₂Sn(OC₄H₉)₂,(C₄H₉)₂Sn(OC₈H₁₇)₂,(C₄H₉)₂Sn (OC₁₂H₂₅)₂,(C₈H₁₇)₂Sn(OCH₃)₂,

Of these, dialkyl tin dialkoxide is more preferable. Especially, dibutyltin dimethoxide is most preferable, because of its low cost and highavailability.

The tetravalent tin compound (C), working as the silanol condensingcatalyst, may be used in combination with another silanol condensingcatalyst, so long as the object of the present invention is attained.

The concrete examples of such silanol condensing catalysts include:

-   -   titanate esters, e.g., those of tetrabutyl titanate and        tetrapropyl titanate;    -   organoaluminum compounds, e.g., aluminum trisacetylacetonate,        aluminum trisethylacetoacetate and diisopropoxy aluminum        ethylacetoacetate;    -   chelate compounds, e.g., zirconium tetraacetylacetonate and        titanium tetraacetylacetonate;    -   lead octylate;    -   amine-based compounds, e.g., butylamine, octylamine,        laurylamine, dibutylamine, monoethanolamine, diethanolamine,        triethanolamine, diethylenetriamine, triethylenetetramine,        oleylamine, cyclohexylamine, benzylamine,        diethylaminopropylamine, xylylenediamine, triethylenediamine,        guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl)        phenol, morpholine, N-methyl morpholine,        2-ethyl-4-methylimidazole, and 1,8-diazabicyclo(5,4,0)        undecene-7 (DBU);    -   salts of these amine-based compounds and carboxylates;    -   low-molecular-weight polyamide resins produced by the reactions        of excessive quantities of polyamines and polybasic acids;    -   products of the reactions between excessive quantities of        polyamines and epoxy compounds; and    -   silane coupling agents containing amino group, e.g.,        γ-aminopropyl trimethoxy silane and N-(β-aminoethyl)aminopropyl        methyldimethoxy silane;    -   and other known silanol condensing catalysts, e.g., acidic and        basic catalysts.

These compounds may be used either individually or in combination.

The tetravalent tin compound (C) is incorporated normally at 0.01 to 50parts by weight per 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1),preferably 0.1 to 20 parts by weight, more preferably 1 to 10 parts byweight. The tetravalent tin compound (C) as the silanol curing catalyst,when used in the above range, sufficiently accelerates the curingreaction at a high speed, and gives the good cured product withoutcausing local heat or foaming while the rubber composition is beingcured. Moreover, the composition has a relatively long pot life, andgood workability.

Silicon Compound (B2)

The curable rubber composition (2) of the present invention may beincorporated with a silicon compound (B2) having no silanol groupsrepresented by the following general formula [V], in order to furtherenhance activity of the tetravalent tin compound (C) as the silanolcondensing catalyst:R⁴ _(a)Si(OR⁵)_(4-a)  [V]wherein, R⁴ and R⁵ are each a hydrocarbon group of 1 to 20 carbon atomswhich may be substituted or not, and “a” is 0, 1, 2, or 3.

The concrete examples of the silicon compounds (C) useful for thepresent invention include:

-   -   (CH₃)₃SiOCH₃, (CH₃)₂Si(OCH₃)₂, (CH₃)₃SiOC₂H₅, (CH₃)₂Si(OC₂H₅)₂,        (CH₃)₃SiOC₆H₅, (CH₃)₂Si(OC₆H₅)₂, (C₆H₅)₃SiOCH₃,        (C₆H₅)₂Si(OCH₃)₂, (C₆H₅)₃SiOC₂H₅, (C₆H₅)₂Si(OC₂H₅)₂,        (C₆H₅)₃SiOC₆H₅, (C₆H₅)₂Si(OC₆H₅)₂, CH₃Si(OCH₃)₃, C₆H₅Si(OCH₃)₃,        CH₃Si(OC₂H₅)₃, C₆H₅Si(OC₂H₅)₃, CH₃Si(OC₆H₅)₃, C₆H₅Si(OC₆H₅)₃,        C₆H₅Si(CH₃)(OCH₃)₂, (C₆H₅)₂Si(CH₃)(OC₆H₅), C₆H₅Si(CH₃)₂(OCH₃),        (C₆H₅)₂Si(CH₃)(OCH₃), (C₆H₅)₂Si (OC₄H₉)₂, (C₄H₉)₂Si(OC₆H₅)₂,        (C₆H₅)₂Si(OC₈H₁₇)₂, (C₈H₁₇)₂Si (OC₆H₅)₂, (C₆H₅)₂Si(OC₁₂H₂₅)₂,        (C₁₂H₂₅)₂Si(OC₆H₅)₂, (CH₃)₂Si(OC₄H₉)₂, (C₂H₅)₃SiOCH₃,        (CH₃)₂Si(OC₈H₁₇)₂, (C₂H₅)₂Si(OCH₃)₂, (CH₃)₂Si(OC₁₂H₂₅)₂,        C₂H₅Si(OCH₃)₃,

Of these compounds, those represented by the general formula [V] with R⁴of an aryl group of 6 to 20 carbon atoms are more preferable, because oftheir notable effect of accelerating curing of the composition. Thesecompounds include phenyltrimethoxysilane, phenylmethyldimethoxysilane,phenyldimethylmethoxysilane, diphenyldimethoxysilane,diphenyldiethoxysilane and triphenylmethoxysilane. Especially,diphenyldimethoxysilane and diphenyldiethoxysilane are most preferable,because of their low cost and high availability.

The silicon compound (B2) is incorporated normally at 0.001 to 50 partsby weight per 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1),preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 partsby weight. The silicon compound (B2), when used in the above range,brings the notable effect of accelerating curing of the compositionwithout deteriorating hardness and tensile strength of the curedproduct.

Other Components

The curable rubber composition of the present invention (2) may beincorporated, as required, with one or more additives within limits notdetrimental to the object of the present invention. These additivesuseful for the present invention include silane coupling agentcontaining isocyanate group, anti-settling agent and leveling agent;cellulose, nitrocellulose and cellulose acetate butyrate; resin, e.g.,alkyd, acrylic, vinyl chloride, chlorinated propylene, chlorinatedrubber and polyvinyl butyral resin; adhesion improver; propertyadjuster; storage stability improver; plasticizer; filler; aginginhibitor; ultraviolet ray absorber; metal deactivator; ozone-causedaging inhibitor; light stabilizer; amine-based radical chaininginhibitor; phosphorus-based peroxide decomposer; lubricant; pigment; andfoaming agent.

The silane coupling agent containing isocyanate group can improveadhesion strength of the cured silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1) toan object or base.

The silane coupling agent containing isocyanate group is a compoundhaving a silicon atom containing group with a hydrolyzable group bondedto the silicon atom (hydrolyzable silicon group) and isocyanate group.The concrete examples of the hydrolyzable silicon group are thoserepresented by the general formula [III] with X of hydrolyzable group,i.e., hydride, halogen, alkoxyl, acyloxy, ketoxymate, amide, acid amide,aminoxy, thioalkoxy or amino group. Of these, a silicon group having analkoxyl group, e.g., methoxy or ethoxy, is more preferable for speed ofhydrolysis. The silane coupling agent has preferably 2 or morehydrolyzable groups, more preferably 3 or more.

The concrete examples of the silane coupling agent containing isocyanategroup useful for the present invention include γ-isocyanatepropyltrimethoxysilane, γ-isocyanate propyltriethoxysilane, γ-isocyanatepropylmethyldiethoxysilane and γ-isocyanate propylmethyldimethoxysilane.

The curable rubber composition (2) of the present invention may befurther incorporated with a silane coupling agent other than the onecontaining isocyanate group or a tackifier other than a silane couplingagent.

The silane coupling agents free of isocyanate group useful for thepresent invention include silanes containing amino group, e.g.,γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane,γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane,γ-(2-aminoethyl) aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyltriethoxysilane, γ-(2-aminoethyl)aminopropylmethyldiethoxysilane, γ-ureidepropyltrimethoxysilane,N-phenyl-γ-aminopropyltrimethoxysilane,N-benzyl-γ-aminopropyltrimethoxysilane andN-vinylbenzyl-γ-aminopropyltriethoxysilane;

-   -   mercapto-containing silanes, e.g.,        γ-mercaptopropyltrimethoxysilane,        γ-mercaptopropyltriethoxysilane,        γ-mercaptopropylmethyldimethoxysilane and        γ-mercaptopropylmethyldiethoxysilane;    -   epoxy-containing silanes, e.g.,        γ-glycidoxypropyltrimethoxysilane,        γ-glycidoxypropyltriethoxysilane,        γ-glycidoxypropylmethyldimethoxysilane,        β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and        β-(3,4-epoxycyclohexyl)ethyltriethoxysilane;    -   carboxysilanes, e.g., β-carboxyethyltriethoxysilane,        β-carboxyethylphenylbis(2-methoxyethoxy)silane and        N-β-(carboxymethyl)aminoethyl-γ-aminopropyltrimethoxysilane;    -   silanes containing a vinyl type unsaturated group, e.g.,        vinyltrimethoxysilane, vinyltriethoxysilane,        γ-methacryloyloxypropylmethyldimethoxysilane and        γ-acryloyloxypropylmethyltriethoxysilane;    -   halogen-containing silanes, e.g.,        γ-chloropropyltrimethoxysilane; and    -   silane isocyanurates, e.g., tris(trimethoxysilyl)isocyanurate.

The derivatives produced by modifying some of the above may be also usedas the silane coupling agents. They include amino-modified silylpolymer, silylated aminopolymer, unsaturated aminosilane complex,phenylaminoalkyl(long chain)silane, aminosilylated silicone, andsilylated polyester.

The above isocyanate-containing silane coupling agents may be usedeither individually or in combination.

The isocyanate-containing silane coupling agent is incorporated normallyat 0.1 to 20 parts by weight per 100 parts by weight of thesilyl-containing

-   -   ethylene/α-olefin/non-conjugated polyene random copolymer rubber        (A1), preferably 0.2 to 15 parts by weight, more preferably 0.5        to 10 parts by weight.

The isocyanate-containing silane coupling agent, when incorporated inthe curable rubber composition (2) of the present invention, bringsabout the effects of significantly improving adhesion of the compositionto a variety of objects, e.g., in organic bases of glass, aluminum,stainless steel, zinc, copper and mortar, and organic bases of vinylchloride, acrylic resin, polyester, polyethylene, polypropylene andpolycarbonate, in the presence or absence of a primer, inter alia moresignificantly in the absence of a primer.

For the adhesion improvers, the commonly used adhesives, silane couplingagents (e.g., aminosilane and epoxysilane compounds) and others may beused. The concrete examples of the adhesion improvers include phenolresin, epoxy resin, γ-aminopropyl trimethoxy silane,N-(β-aminoethyl)aminopropyl methyldimethoxy silane, coumarone/indeneresin, rosin ester resin, terpene/phenol resin, α-methyl styrene/vinyltoluene copolymer, polyethylmethyl styrene, alkyl titanate, and aromaticpolyisocyanate. The adhesion improver is incorporated preferably atabout 1 to 50 parts by weight per 100 parts by weight of thesilyl-containing

-   -   ethylene/α-olefin/non-conjugated polyene random copolymer rubber        (A1), more preferably 5 to 30 parts by weight.

The storage stability improvers useful for the present invention includecompounds with silicon to which a hydrolyzable group is bonded andesters of ortho-organic acids. The concrete examples of the storagestability improvers include methyltrimethoxy silane, methyltriethoxysilane, tetramethoxy silane, ethyltrimethoxy silane, dimethyldiethoxysilane, trimethylisobutoxy silane, trimethyl(n-butoxy) silane,n-butyltrimethoxy silane, and methyl ortho-formate.

The storage stability improver is incorporated preferably at about 0.5to 20 parts by weight per 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1),more preferably 1 to 10 parts by weight.

The plasticizer useful for the present invention is also not limited,and any commonly used one may be used. However, it is preferably the onecompatible with each component for the curable rubber composition (2) ofthe present invention.

The concrete examples of these plasticizers include:

-   -   hydrocarbon-based compounds, e.g., polybutene, hydrogenated        polybutene, ethylene/α-olefin co-oligomer, α-methyl styrene        oligomer, biphenyl, triphenyl, triaryl dimethane, alkylene        triphenyl, liquid polybutadiene, hydrogenated liquid        polybutadiene, alkyl diphenyl, partially hydrogenated        ter-phenyl, paraffin oil, naphthene oil and atactic        polypropylene;    -   parafin chlorides;    -   phthalate esters, e.g., dibutyl phthalate, diheptyl phthalate,        di(2-ethylhexyl) phthalate, butyl benzyl phthalate and bytyl        phthalyl butyl glycolate;    -   non-aromatic, dibasic acid esters, e.g., dioctyl adipate and        dioctyl cebacate;    -   esters of polyalkylene glycol, e.g., diethylene glycol        dibenzoate and triethylene glycol dibenzoate; and    -   phosphate esters, e.g., tricresyl phosphate and tributyl        phosphate.

Of these, saturated hydrocarbon-based compounds are more preferable.They may be used either individually or in combination.

Of the above-described compounds, hydrocarbon-based compounds free ofunsaturated group, e.g., hydrogenated polybutene, hydrogenated liquidpolybutadiene, paraffin oil, naphthene oil and atactic polypropylene,are more preferable for various reasons, e.g., high compatibility witheach component for the rubber composition of the present invention,limited effects on curing speed of the rubber composition, goodresistance to weather of the cured product, and cheapness.

The plasticizer may be used in place of the solvent during the processof introducing a hydrolyzable silyl group into the above-describedethylene/α-olefin/non-conjugated polyene random copolymer rubber (A₀),for the purposes of, e.g., adjusting reaction temperature and viscosityof the reaction system.

The plasticizer is incorporated preferably at about 10 to 500 parts byweight per 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1),more preferably about 20 to 300 parts.

The concrete examples of the fillers described above include woodpowder, pulp, cotton chips, asbestos, glass fibers, carbon fibers, mica,walnut shell powder, graphite, diatomaceous earth, white clay, fumedsilica, settling silica, silicic anhydride, carbon black, calciumcarbonate, clay, talc, titanium oxide, magnesium carbonate, quartz, finealuminum powder, flint powder, and zinc powder. Of these, morepreferable ones are thixotropic fillers, e.g., settling silica, fumedsilica and carbon black; and calcium carbonate, titanium oxide and talc.

The filler, when used, is incorporated preferably at about 10 to 500parts by weight per 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1),more preferably about 20 to 300 parts by weight.

The aging inhibitors useful for the present invention include commonlyused known sulfur-based ones, radical inhibitors and ultraviolet rayabsorbers.

The sulfur-based aging inhibitors useful for the present inventioninclude mercaptans, salts thereof, sulfides including sulfidecarboxylate esters and hindered phenol-based sulfides, polysulfides,dithiocarboxylates, thioureas, thiophosphates, sulfonium compounds,thioaldehydes, thioketones, mercaptals, monothio acids, polythio acids,thioamides, and sulfoxides.

More concretely, the sulfur-based aging inhibitors include:

-   -   mercaptans, e.g., 2-mercaptobenzothiazole; salts of mercaptans,        e.g., zinc salt of 2-mercaptobenzothiazole;    -   sulfides, e.g., 4,4′-thio-bis(3-methyl-6-t-butyl phenol),        4,4′-thio-bis(2-methyl-6-t-butyl phenol),        2,2′-thio-bis(4-methyl-6-t-butyl phenol),        bis(3-methyl-4-hydroxy-5-t-butylbenzyl) sulfide, terephthaloyl        di(2,6-di-methyl-4-t-butyl-3-hydroxybenzyl) sulfide,        phenothiazine, 2,2′-thio-bis-(4-octylphenol) nickel, dilauryl        thiodipropionate, distearyl thiodipropionate, dimyristyl        thiodipropionate, ditridecyl thiodipropionate,        distearylβ,β′-thiodibutyrate, lauryl-stearylthiodipropionate and        2,2-thio[diethyl-bis-3(3,5-di-t-butyl-4-hydroxy        phenol)propionate];    -   polysulfides, e.g., 2-benzothiazole disulfide;    -   dithiocarboxylates, e.g., zinc dibutyldithiocarbamate, zinc        diethyldithiocarbamate, nickel dibutyldithiocarbamate, zinc        di-n-butyldithiocarbamate, dibutyl ammonium        dibutyldithiocarbamate, zinc ethyl-phenyl-dithiocarbamate and        zinc dimethylcarbamate;    -   thioureas, e.g., 1-butyl-3-oxy-diethylene-2-thiourea,        di-o-tolyl-thiourea and ethylene thiourea; and    -   thiophosphates, e.g., trilauryltrithiophosphate.

The above-described sulfur-based aging inhibitor preventsdecomposition/aging of the main chain under heating much moreefficiently than the other types for the curable rubber composition ofthe present invention, controlling the problems, e.g., residual surfacetackiness.

The radical inhibitors useful for the present invention includephenol-based ones, e.g., 2,2-methylene-bis(4-methyl-6-t-butyl phenol)and tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propio nate]methane; and amine-based ones, e.g., phenyl-β-naphthylamine,α-naphthylamine and N,N′-sec-butyl-p-phenylenediamine, phenothiazine andN,N′-diphenyl-p-phenylenediamine.

The ultraviolet ray absorbers useful for the present invention include2-(2′-hydroxy-3′,5′-di-t-butylphenyl) benzotriazole andbis(2,2,6,6-tetramethyl-4-piperidine) cebacate.

The aging inhibitor is incorporated at about 0.1 to 20 parts by weightper 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1),preferably 1 to 10 parts by weight.

The curability improving effect by the combination of the tetravalenttin compound (C) and silicon compound (B2), represented by the generalformula [V], for the present invention is similarly observed,irrespective of the presence or absence of the isocyanate-containingsilane coupling agent, which is used for the present invention asrequired.

Improvement of curability is also observed, when various additivesdescribed above are incorporated. More concretely, the curable rubbercomposition (2) of the present invention can be cured notably faster ifincorporated with the above-described additives, when the composition(2) is used as an elastomer sealant for construction, and sealant forlaminated glass and electric/electronic device members, e.g., back sideof a solar cell; electrical insulator for insulating coatings of wiresand cables; tackifier and adhesive; and sealant that makes the edge (cutsection) of net-reinforced or laminated glass rust-preventive andwater-proof.

Curable Rubber Composition (2) and its Uses

The curable rubber composition (2) of the present invention contains thecurable composition with the hydrolyzable silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber as thecomponent (A1). More concretely, it contains the organic polymer (Z)containing the hydrolyzable silyl group represented by the generalformula [III] and essentially no unsaturated double bonds in the mainchain, a tetravalent tin compound (C), a specific silicon compound (B1)and, as required, a silane coupling agent containing isocyanate group.It can be suitably used for electric/electronic device members,transportation machines, and civil engineering/construction, medical andleisure areas, as described earlier.

The curable rubber composition (2) of the present invention can be usedas a sealant, a potting agent, a coating material or an adhesive forelectric/electronic device members, transportation machines, and civilengineering/construction, medical and leisure areas.

Curable Composition (3)

The curable composition (3) of the present invention contains (a) thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1) and (b) a silicon compound (B3) having at leastone amino group and at least one trialkylsiloxy group in the molecule.

The silyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1) as the component (a) has an intrinsic viscosity[η] of around 0.001 to 2 dl/g, preferably 0.01 to 1 dl/g, morepreferably 0.05 to 1 dl/g, still more preferably 0.05 to 0.7 dl/g, stillmore preferably 0.1 to 0.5 dl/g. It is recommended that the copolymerrubber has at least 0.1 reactive silicon group per the polymer molecule,preferably 0.5 to 20. When the number of the reactive silicon grouppresent in the molecule is less than 0.1, the copolymer rubber will beinsufficient in curability. When it is excessively large, on the otherhand, the copolymer rubber cannot have good mechanical properties,because of the resultant excessively tight network structure.

Silicon Compound (B3)

The silicon compound (B3) for the present invention having at least oneamino group and at least one trialkylsiloxy group in the molecule isrepresented by the following general formula:

wherein, Y_(d) is an alkyl group having an amino group; R¹ is an alkylgroup of 1 to 20 carbon atoms, aryl group of 6 to 20 carbon atoms,aralkyl group of 7 to 20 carbon atoms, or triorganosiloxy grouprepresented by the formula R⁵ ₃SiO— (wherein, R⁵ is a monovalenthydrocarbon group of 1 to 20 carbon atoms, three R⁵'s may be the same ordifferent), which may be the same or different when there are 2 or moreR¹'s; X is a hydroxyl group, a similar or dissimilar hydrolyzable groupor the group represented by —O—SiQ₃, wherein Q is a group selected fromthe group consisting of hydroxyl, similar or dissimilar hydrolyzablegroup, a monovalent organic group of 1 to 20 carbon atoms, which may besubstituted or not substituted and triorganosiloxy; and contains atleast one hydroxyl, or a similar or dissimilar hydrolyzable group; R²,R³ and R⁴ are each an alkyl group of 1 to 6 carbon atoms or phenylgroup, which may be substituted or not substituted; and “c” is aninteger of 0 to 2 and “d” and “e” are 1 or 2, respectively.

The examples of these compounds includeγ-aminopropyltrimethylsiloxydiethoxysilane,N-(β-aminoethyl)-γ-aminopropyltrimethylsiloxydimethoxysilane,N-(β-aminoethyl)-γ-aminopropyltrimethylsiloxymethylmethoxysilane,diethylenetriaminopropyltrimethylsiloxydimethoxysilane,N,N-dimethyl-γ-aminopropyltrimethylsiloxydimethoxysilane. Theabove-described compound can be easily synthesized by reacting a siliconcompound having at least one amino group and at least one hydrolyzablegroup in the molecule with a trialkylsilanol Ae compound.

The examples of the silicon compounds having at least one amino groupand at least one hydrolyzable group in the molecule include, but notlimited to, γ-aminopropyltriethoxylsilane (Nippon Unicar Co., Ltd.,A-1100), N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (Nippon UnicarCo., Ltd., A-1120), N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane(Shin-Etsu Chemical Co., Ltd., KBM-602),diethylenetriaminopropyltrimethoxysilane (Nippon Unicar Co., Ltd.,A-1130), N,N-dimethyl-γ-aminopropyltrimethyoxy silane (Chisso, D5200),N,N′-bis[γ-trimethoxysilylpropyl]ethylenediamine (Chisso, XS1003),N-benzyl-γ-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.,X-12-512), and N-phenyl-γ-aminopropyltrimethoxysilane (Shin-EtsuChemical Co., Ltd., KBM573).

The examples of the trialkyl silanol compounds include, but not limitedto, trimethyl silanol, triethyl silanol and triphenyl silanol.

Other Components

The curable composition (3) of the present invention may beincorporated, as required, with one or more plasticizers of varioustypes. The plasticizer(s) can give good results, when incorporated at 0to 300 parts by weight as the total quantity per 100 parts by weight ofthe silyl-containing

-   -   ethylene/α-olefin/non-conjugated polyene random copolymer rubber        (A1). The improvement effect will be rarely observed, when the        total quantity of plasticizer(s) exceeds 300 parts, because of        excessive content of the liquid component.

The plasticizers useful for the present invention include phthalateesters, e.g., those of dioctyl phthalate, diisodecyl phthalate, dibutylphthalate and butyl benzyl phthalate; epoxy plasticizers, e.g.,epoxidized soybean oil, epoxidized linseed oil and benzyl epoxystearate;polyester-based plasticizers, e.g., polyesters of a dibasic acid anddivalent alcohol; polyethers, e.g., polypropylene glycol and derivativesthereof; hydrocarbon-based plasticizers, e.g., polybutene,ethylene/α-olefin oligomer, polystyrene, α-methyl styrene oligomer,biphenyl, triphenyl, triaryl dimethane, alkylene triphenyl, liquidpolybutadiene, hydrogenated liquid polybutadiene, alkyl diphenyl,partially hydrogenated ter-phenyl, paraffin oil, naphthene oil andatactic polypropylene; and polychloroprene, polyisoprene and chlorinatedparaffins. These compounds may be used either individually or incombination of any form.

These compounds may be used either individually or in combination. Ofthese, the hydrocarbon-based compounds free of unsaturated group (e.g.,hydrogenated polybutene, hydrogenated liquid polybutadiene, paraffinoil, naphthene oil and atactic polypropylene) are more preferable,because they are well compatible with various components for the curablecomposition (3) of the present invention, affecting curing speed of therubber composition to only a limited extent, giving the cured product ofhigh resistance to weather, and inexpensive. The above plasticizer mayreplace the solvent used when a reactive silicon group is introduced inthe saturated hydrocarbon-based polymer, in order to adjust reactiontemperature and viscosity of the reaction system.

The composition (3) of the present invention may be incorporated with asilanol condensing catalyst, in order to accelerate the reactions of thehydrolyzable silyl group.

The concrete examples of the silanol condensing catalysts useful for thepresent invention include titanate esters, e.g., those of tetrabutyltitanate and tetrapropyl titanate; organotin compounds, e.g., dibutyltin dilaurate, dibutyl tin maleate, dibutyl tin diacetate, tin octylate,tin naphthenate, product of the reaction between dibutyl tin oxide andphthalate ester, and dibutyl tin diacetylacetonate; organoaluminumcompounds, e.g., aluminum trisacetylacetonate, aluminumtrisethylacetoacetate and diisopropoxy aluminum ethylacetoacetate;products by the reactions between a bismuth salt and organocarboxylicacid, e.g., bismuth-tris(2-ethylhexoate) and bismuth-tris(neodecanoate);chelate compounds, e.g., zirconium tetraacetylacetonate and titaniumtetraacetylacetonate; organolead compounds, e.g., lead octylate;organovanadium compounds, amine-based compounds, and salts of thesecompounds and carboxylates, e.g., butylamine, octylamine, dibutylamine,monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine,triethylenetetramine, oleylamine, cyclohexylamine, benzylamine,diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine,diphenylguanidine, 2,4,6-tris(dimethylaminomethyl) phenol, morpholine,N-methyl morpholine, 2-ethyl-4-methylimidazole and1,8-diazabicyclo(5,4,0) undecene-7 (DBU); low-molecular-weight polyamideresins produced by the reactions between excessive quantities ofpolyamines and polybasic acids; and products of the reactions betweenexcessive quantities of polyamines and epoxy compounds. The silanolcondensing catalysts useful for the present invention are not limited tothe above, and include the commonly used condensing catalysts. Thesesilanol condensing catalysts may be used either individually or incombination. Of these silanol condensing catalysts, more preferable onesare organometal compounds, and combinations of organometal compounds andamine-based compounds, viewed from curability of the composition.

The silanol condensing catalyst is incorporated preferably at about 0.1to 50 parts by weight per 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1),more preferably 0.2 to 20 parts by weight. It is undesirable that thecatalyst content relative to the copolymer rubber (A1) is below theabove range, because of insufficient curing speed and insufficientextent of the curing reaction, and beyond the above range is alsoundesirable, because of local heating or foaming occurring during thecuring process to make it difficult to produce the cured product of goodproperties.

The composition (3) of the present invention may be adequatelyincorporated, as required, with various additives, e.g., dehydrator,compatibilizer, adhesion improver, property adjuster, storage stabilityimprover, filler, aging inhibitor, ultraviolet ray absorber, metaldeactivator, ozone-induced aging inhibitor, light stabilizer,amine-based radical chaining inhibitor, phosphorus-based peroxidedecomposer, lubricant, pigment, foaming agent, flame retardant,anti-static agent, and silane compound.

The adhesion improvers useful for the present invention include commonlyused adhesives, silane coupling agents, e.g., aminosilane compounds andepoxysilane compounds; and others. The concrete examples of theseadhesion improvers include phenolic resin, epoxy resin, γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)aminopropyl methyldimethoxysilane,coumarone/indene resin, rosin ester resin, terpene/phenol resin,α-methyl styrene/vinyl toluene copolymer, polyethylmethyl styrene, alkyltitanates, and aromatic polyisocyanate. The adhesion improver isincorporated preferably at about 1 to 50 parts by weight per 100 partsby weight of total of the components (A1) and (B3), more preferably 5 to30 parts by weight.

The storage stability improvers useful for the present invention includecompounds with silicon to which a hydrolyzable group is bonded andesters of ortho-organic acids. The concrete examples of the storagestability improvers include methyltrimethoxy silane, methyltriethoxysilane, tetramethoxy silane, ethyltrimethoxy silane, dimethyldiethoxysilane, trimethylisobutoxy silane, trimethyl(n-butoxy) silane,n-butyltrimethoxy silane, and methyl ortho-formate.

The concrete examples of the fillers include wood powder, pulp, cottonchips, asbestos, glass fibers, carbon fibers, mica, walnut shell powder,rice hull powder, graphite, diatomaceous earth, white clay, fumedsilica, settling silica, silicic anhydride, carbon black, calciumcarbonate, clay, kaolin, talc, titanium oxide, magnesium carbonate,quartz powder, glass beads, fine aluminum powder, flint powder, and zincpowder. Of these, more preferable ones are thixotropic fillers, e.g.,settling silica, fumed silica and carbon black; and calcium carbonate,titanium oxide and talc. They may be used either individually or incombination.

The aging inhibitors useful for the present invention include commonlyused known ones, e.g., sulfur-based ones, radical inhibitors andultraviolet ray absorbers.

The sulfur-based aging inhibitors useful for the present inventioninclude mercaptans, salts thereof, sulfides including sulfidecarboxylate esters and hindered phenol-based sulfides, polysulfides,dithiocarboxylates, thioureas, thiophosphates, sulfonium compounds,thioaldehydes, thioketones, mercaptals, mercaptols, monothio acids,polythio acids, thioamides, and sulfoxides. More concretely, thesulfur-based aging inhibitors include mercaptans, e.g.,2-mercaptobenzothiazole; salts of mercaptans, e.g., zinc salt of2-mercaptobenzothiazole; sulfides, e.g.,4,4′-thio-bis(3-methyl-6-t-butyl phenol),4,4′-thio-bis(2-methyl-6-t-butyl phenol),2,2′-thio-bis(4-methyl-6-t-butyl phenol),bis(3-methyl-4-hydroxy-5-t-butylbenzyl) sulfide,terephthaloyldi(2,6-dimethyl-4-t-butyl-3-hydroxybenzyl) sulfide,phenothiazine, 2,2′-thio-bis (4-octyl phenol) nickel, dilaurylthiodipropionate, distearyl thiodipropionate, dimyristylthiodipropionate, ditridecyl thiodipropionate,distearylβ,β′-thiodibutyrate, lauryl-stearyl thiodipropionate and2,2-thic[diethyl-bis-3-(3,5-di-t-butyl-4-hydroxy phenol)propionate];polysulfides, e.g., 2-benzothiazole disulfide; dithiocarboxylates, e.g.,zinc dibutyldithiocarbamate, zinc diethyldithiocarbamate, nickeldibutyldithiocarbamate, zinc di-n-butyldithiocarbamate, dibutyl ammoniumdibutyldithiocarbamate, zinc ethyl-phenyl-dithiocarbamate and zincdimethyldithiocarbamate; thioureas, e.g.,1-butyl-3-oxy-diethylene-2-thiourea, di-o-tolyl-thiourea and ethylenethiourea; and thiophosphates, e.g., trilauryltrithiophosphate.

The above-described sulfur-based aging inhibitor preventsdecomposition/aging of the main chain under heating much moreefficiently than the other types for the composition (3) of the presentinvention, controlling the problems, e.g., residual surface tackiness.

The radical inhibitors useful for the present invention includephenol-based ones, e.g., 2,2-methylene-bis(4-methyl-6-t-butyl phenol)and tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propio nate]methane; and amine-based ones, e.g., phenyl-β-naphthylamine,α-naphthylamine, N,N′-sec-butyl-p-phenylenediamine, phenothiazine andN,N′-diphenyl-p-phenylenediamine.

The ultraviolet ray absorbers useful for the present invention include2-(2′-hydroxy-3′,5′-di-t-butylphenyl) benzotriazole andbis(2,2,6,6-tetramethyl-4-piperidine) cebacate.

The curable composition (3) of the present invention may be incorporatedwith a polymer having a reactive silicon group other than the component(a) the ethylene/α-olefin/non-conjugated polyene random copolymer rubbercontaining a hydrolyzable silyl group (A1), e.g., polydimethyl siloxane.

The method of producing the composition (3) of the present invention,composed of (a) the hydrolyzable silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1)and (b) the silicon compound (B3), is not limited. More concretely, thecomponent (b) is incorporated and uniformly dispersed in the component(a) while adequately controlling the conditions, e.g., stirringconditions, if required. These components may be also mixed with eachother by a mixer, roll or kneader.

The composition thus prepared is applicable to one-liquid type curablecomposition, to say nothing of two-liquid type. For the one-liquid type,the composition of the present invention is prepared in an essentiallymoisture-free condition. It can withstand storage for extended periodswhen kept in a closed condition, and quickly starts curing from thesurface when exposed to the atmosphere.

The curable composition (3) of the present invention is useful as anelastomer sealant for building structures, civil engineering works, andother industrial areas, and also can find use as paints, adhesives,impregnating agents and coating materials.

Curable Rubber Composition (3) and its Uses

The curable rubber composition (3) of the present invention contains thecurable composition with the hydrolyzable silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber as thecomponent (A1). More concretely, it contains

-   (a) the organic polymer (Z) and-   (b) the silicon compound having at least one amino group and at    least one trialkylsiloxy group in the molecule (B3), and is suitably    used for electric/electronic device members, transportation    machines, and civil engineering/construction, medical and leisure    areas, as described earlier.

The curable composition (3) of the present invention can be used assealants, potting agents, coating materials or adhesives forelectric/electronic device members, transportation machines, and civilengineering/construction, medical and leisure areas.

In other words, the present invention provides sealants, potting agents,coating materials and adhesives, composed of the curable compositionwhich comprises (a) the organic polymer (Z) and (b) the silicon compoundhaving at least one amino group and at least one trialkylsiloxy group inthe molecule (B3).

Curable Composition (4)

The curable composition (4) of the present invention contains (a) thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1) and (b) an organosilicon compound (B4).

Organosilicon Compound (B4)

The organosilicon compound (B4) for the present invention is representedby the following general formula [VI]:(R²(CH₃)₂SiO)_(n)R¹  [VI]wherein, R¹ is an alcohol residue or weak acid residue; R² is methyl orvinyl group; and “n” is a positive integer.

R¹ in the general formula [VI] is preferably a mono- to tri-valentalcohol residue or a weak acid residue, wherein the term alcohol residuemeans a monovalent or polyhydric alcohol partly or totally left by itshydroxyl group, while weak acid residue means a monovalent or polyvalentweak acid partly or totally left by its hydroxyl group. The residue maybe a compound simultaneously having hydroxyl group and a weak acid group(e.g., carboxyl) partly or totally left by its hydroxyl group.

The concrete examples of alcohols and weak acids which can berepresented by R¹ include aliphatic alcohols of 30 or less carbon atoms,which may be substituted or not substituted, e.g., methanol, ethanol,n-butanol, i-butanol, n-pentanol, i-pentanol, ethylene chlorohydrin,benzyl alcohol, cyclohexanol, 3-chloropropanol, ethylene glycol,propanediol, propylene glycol, butanediol, glycerin and acetylacetone(tautomers); aromatic hydroxy compounds of 6 to 30 carbon atoms, whichmay be substituted or not substituted, e.g., phenol, cresol,chlorophenol, bisphenol A, naphthol, hydroquinone andhydronaphthoquinone; aliphatic and aromatic carboxylic acids of 30 orless carbon atoms, which may be substituted or not substituted, e.g.,formic, acetic, propionic, butyric, valeric, capric, caproic, lauric,palmitic, stearic, oleic, heptacosanoic, behenic, melissic, acrylic,undecylenic, sorbic, linolic, linolenic, arachidonic, propiolic,stearolic, oxalic, malonic, succinic, glutaric, adipic, maleic, fumaric,itaconic, benzoic, phthalic, terephthalic, trimellitic, chlorobenzoic,toluyl, oxypropionic, oxybenzoic and oxytoluyl acids; diethylene glycol,triethylene glycol, polyethylene glycol, polypropylene glycol,polybutadiene having hydroxyl or carboxyl group, hydrogenatedpolybutadiene having hydroxyl or carboxyl group, polyethyleneterephthalate and polybutylene terephthalate having hydroxyl and/orcarboxyl group; and inorganic acids, e.g., boric and carbonic acids.

Of these alcohols and weak acids, the organic compounds are preferablyfree of hetero atoms other than oxygen and halogen.

The organosilicon compound (B4) having phenyl group as R¹, which may besubstituted or not substituted, is particularly preferable, because ofits wide availability and good effects it brings.

The weak acid in this specification is defined as the acid having a pKaof 1 or more, preferably 2 or more, more preferably 3 or more, whendissolved in water.

R² in the general formula [VI] is methyl or vinyl (CH₂═CH—) group. Anyother group is not desirable for R², because it may not sufficientlyachieve the objects of the present invention. Methyl group is morepreferable, because of its wider availability.

The concrete examples of the suitable organosilicon compounds (B4)include CH₃OSi(CH₃)₃, CH₃CH₂OSi (CH₃)₃, ClCH₂CH₂OSi(CH₃)₃,

Of these compounds, more preferable ones are those having a molecularweight of 140 or more, still more preferably 150 or more, viewed fromimprovement in modulus and elongation. The most preferable one is

because of its wider availability. The upper limit of the molecularweight of the organosilicon compound (B4) is not limited, but it ispreferably 5,000 or less, more preferably 2,000 or less.

Content of the organosilicon compound (B4) should be adequately selectedfor the specific properties the cured product is expected to have. It isincorporated normally at 0.1 to 50 parts by weight per 100 parts byweight of the silyl-containing ethylene/α-olefin/non-conjugated polyenerandom copolymer rubber (A1), preferably 1 to 20 parts by weight.

The organosilicon compound (B4) is hydrolyzed while the composition iscured to form the silanol compound, which reacts with the hydrolyzablesilyl group or hydrolyzed hydrolyzable group in the copolymer rubber(A1).

The method of mixing the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1)and organosilicon compound (B4) with each other is not limited, so longas the component (B4) is uniformly dissolved or dispersed in thecomponent (A1) by carefully setting the conditions, e.g., temperatureand stirring conditions, as required. In this case, the composition maynot be necessarily transparent completely, and can sufficiently achievethe objectives even when it is not transparent, so long as thecomposition (B4) is dispersed almost uniformly. A dispersibilityimprover, e.g., surfactant, may be used, as required.

Other Components

The curable composition (4) of the present invention may beincorporated, as required, with various additives, e.g., white carbon,carbon black, calcium carbonate, titanium oxide, talc, asbestos andglass fibers, which serve, e.g., as a reinforcing or non-reinforcingfiller, a plasticizer, an antioxidant, an ultraviolet ray absorber, apigment, or a flame retardant, to be useful as adhesives, tackifiers,paints, sealant compositions, waterproof materials, spray materials,shaping materials or casting rubber materials. Of these, application tosealant compositions is especially useful.

The curable composition (4) of the present invention, when used as asealant, may be incorporated, as required, with a plasticizer, filler,reinforcing agent, dripping inhibitor, colorant, aging inhibitor,adhesion promoter, curing catalyst or property adjuster.

The plasticizers useful for the present invention include phthalateesters, e.g., those of dibutyl phthalate, diheptyl phthalate,di(2-ethylhexyl) phthalate, butyl benzyl phthalate and butyl phthalylbutyl glycolate; non-aromatic, dibasic acid esters, e.g., those ofdioctyl adipate and dioctyl cebacate; esters of polyalkylene glycol,e.g., those of diethylene glycol dibenzoate and triethylene glycoldibenzoate; phosphate esters, e.g., those of tricresyl phosphate andtributyl phosphate; chlorinated paraffins; and

-   -   hydrocarbon-based compounds, e.g., alkyl diphenyl, polybutene,        hydrogenated polybutene, ethylene/α-olefin oligomer, α-methyl        styrene oligomer, biphenyl, triphenyl, triaryl dimethane,        alkylene triphenyl, liquid polybutadiene, hydrogenated liquid        polybutadiene, paraffin oil, naphthene oil and atactic        polypropylene. The above compound is selected, depending on        specific purposes, e.g., adjustment of characteristics and        properties. They may be used either individually or in        combination, although not necessarily essential. The plasticizer        may be incorporated, while the polymer is produced.

Of these, the hydrocarbon-based compounds free of unsaturated groups(e.g., hydrogenated polybutene, hydrogenated liquid polybutadiene,paraffin oil, naphthene oil and atactic polypropylene) are morepreferable, because they are well compatible with various components forthe composition (4) of the present invention, affecting curing speed ofthe composition to only a limited extent, giving the cured product ofhigh resistance to weather, and inexpensive.

The above plasticizer may replace the solvent used when the reactivesilicon group is introduced in the saturated hydrocarbon-based polymer,to adjust reaction temperature and viscosity of the reaction system.

The fillers and reinforcing agents useful for the present inventioninclude limestone powder and calcium carbonate; calcium carbonatesurface-treated with a fatty acid, a resin acid, or a cationic oranionic surfactant; magnesium carbonate; talc; titanium oxide; bariumsulfate; alumina; powder of metal (e.g., aluminum, zinc or iron);bentonite; kaolin clay; fumed silica; quartz powder; and carbon black.These are the common ones, and one or more of these compounds may beused. Of these, the filler or reinforcing agent capable of impartingtransparency, e.g., fumed silica, can give the sealant with hightransparency.

The dripping inhibitors useful for the present invention include ahydrogenated castor oil derivative; and metallic soaps, e.g., calciumstearate, aluminum stearate and barium stearate. A dripping inhibitormay not be necessary, depending on purposes of the curable composition,and a filler or a reinforcing agent incorporated.

The colorants useful for the present invention include the commoninorganic and organic pigments, and dyes, each of which may be used, asrequired.

The property adjusters useful for the present invention include varioussilane coupling agents: such as alkyl alkoxy silanes, e.g.,methyltrimethoxy silane, dimethyldimethoxy silane, andn-propyltrimethoxy silane; alkyl isopropenoxy silane, e.g.,dimethyldiisopropenoxy silane, methyltriisopropenoxy silane andγ-glycidoxypropylmethyldiisopropenoxy silane; alkoxy silanes having afunctional group, e.g., γ-glycidoxypropylmethyldimethoxy silane,γ-glycidoxypropyltrimethoxy silane, vinyl trimethoxy silane,γ-aminopropyltrimethoxy silane, N-(β-aminoethyl)aminopropylmethyldimethoxy silane, γ-mercaptopropyltrimethoxy silane andγ-mercaptopropylmethyldimethoxy silane; silicone varnishes; andpolysiloxanes.

The above property adjuster can increase hardness, or decrease hardnessand increase elongation of the curable composition (4) of the presentinvention, when it is cured.

Use of an adhesion promoter is not essential, because the polymer of thepresent invention itself is adhesive to glass, other ceramic materialsand metals, and adhesive to materials in a wider range in the presenceof a varying primer. However, the composition can have improved adhesionto materials in a still wider range, when incorporated with one or moretypes of epoxy resin, phenolic resin, various silane coupling agents,alkyl titanate or aromatic polyisocyanate.

The curing catalysts useful for the present invention include: titanateesters, e.g., those of tetrabutyl titanate and tetrapropyl titanate;organotin compounds, e.g., dibutyl tin dilaurate, dibutyl tin maleate,dibutyl tin diacetate, tin octylate and tin naphthenate; lead octylate;amine-based compounds and salts of these compounds and carboxylates,e.g., butylamine, octylamine, dibutylamine, monoethanolamine,diethanolamine, triethanolamine, diethylenetriamine,triethylenetetramine, oleylamine, octylamine, cyclohexylamine,benzylamine, diethylaminopropylamine, xylylenediamine,triethylenediamine, guanidine, diphenylguanidine,2,4,6-tris(dimethylaminomethyl) phenol, morpholine, N-methyl morpholine,and 1,3-diazabicyclo(5,4,6) undecene-7 (DBU); low-molecular-weightpolyamide resins produced by the reactions between excessive quantitiesof polyamines and polybasic acids; products of the reactions betweenexcessive quantities of polyamines and epoxy compounds; and knownsilanol condensing catalysts, e.g., silane coupling agents containingamino group (e.g., γ-aminopropyl trimethoxy silane andN-(β-aminoethyl)aminopropyl methyldimethoxy silane). These compounds maybe used either individually or in combination.

A solvent may be used for, e.g., improving workability and reducingviscosity. The solvents useful for the above purposes include aromatichydrocarbon-based ones, e.g., toluene and xylene; ester-based ones,e.g., ethyl acetate, butyl acetate, amyl acetate and cellosolve acetate;and ketone-based ones, e.g., methylethylketone, methylisobutylketone anddiisobutylketone. The solvent may be used during the process ofproducing the polymer.

The aging inhibitors useful for the present invention include a commonlyused antioxidant, e.g., sulfur-based aging inhibitor, radical inhibitorand ultraviolet ray absorber, although use of the aging inhibitor is notessential.

The sulfur-based aging inhibitors useful for the present inventioninclude mercaptans, salts thereof, sulfides including sulfidecarboxylate esters and hindered phenol-based sulfides, polysulfides,dithiocarboxylates, thioureas, thiophosphates, sulfonium compounds,thioaldehydes, thioketones, mercaptals, mercaptols, monothio acids,polythio acids, thioamides, and sulfoxides.

More concretely, the sulfur-based aging inhibitors include mercaptans,e.g., 2-mercaptobenzothiazole; salts of mercaptans, e.g., zinc salt of2-mercaptobenzothiazole; sulfides, e.g.,4,4′-thio-bis(3-methyl-6-t-butyl phenol),4,4′-thio-bis(2-methyl-6-t-butyl phenol),2,2′-thio-bis(4-methyl-6-t-butyl phenol),bis(3-methyl-4-hydroxy-5-t-butylbenzyl) sulfide,terephthaloyldi(2,6-dimethyl-4-t-butyl-3-hydroxybenzyl) sulfide,phenothiazine, 2,2′-thio-bis (4-octyl phenol) nickel, dilaurylthiodipropionate, distearyl thiodipropionate, dimyristylthiodipropionate, ditridecyl thiodipropionate,distearylβ,β′-thiodibutyrate, lauryl-stearyl thiodipropionate and2,2-thio[diethyl-bis-3-(3,5-di-t-butyl-4-hydroxy phenol)propionate];polysulfides, e.g., 2-benzothiazole disulfide; dithiocarboxylates, e.g.,zinc dibutyldithiocarbamate, zinc diethyldithiocarbamate, nickeldibutyldithiocarbamate, zinc di-n-butyldithiocarbamate, dibutyl ammoniumdibutyldithiocarbamate, zinc ethyl-phenyl-dithiocarbamate and zincdimethyldithiocarbamate; thioureas, e.g.,1-butyl-3-oxy-diethylene-2-thiourea, di-o-tolyl-thiourea and ethylenethiourea; and thiophosphates, e.g., trilauryltrithiophosphate.

The above-described sulfur-based aging inhibitor preventsdecomposition/aging of the main chain under heating much moreefficiently than the other types for the curable composition of thepresent invention, controlling the problems, e.g., residual surfacetackiness.

The radical inhibitors useful for the present invention includephenol-based ones, e.g., 2,2-methylene-bis(4-methyl-6-t-butyl phenol)and tetrakis [methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propio nate]methane; and amine-based ones, e.g., phenyl-β-naphthylamine,α-naphthylamine, N,N′-sec-butyl-p-phenylenediamine, phenothiazine andN,N′-diphenyl-p-phenylenediamine.

The ultraviolet ray absorbers useful for the present invention include2-(2′-hydroxy-3′,5′-di-t-butylphenyl) benzotriazole andbis(2,2,6,6-tetramethyl-4-piperidine) cebacate.

The sealant composition may be prepared for a one-liquid type, where thecomposition of all of the components is prepared beforehand and sealed,and cured with moisture in air after it is applied, or for a two-liquidtype, where the separately prepared curing agent composition of, e.g., acuring catalyst, a filler, a plasticizer and water as the curing agentis mixed with the polymer composition before use.

When the sealant composition is used for the one-liquid type, it ispreferable that the water-containing component is dehydrated/driedbeforehand, or dehydrated during mixing/kneading under a vacuum, becauseit contains all of the components before use.

When used for the two-liquid type, on the other hand, the sealantcomposition may contain water to some extent, because thepolymer-containing main ingredient is not necessarily incorporatedbeforehand with the curing catalyst and hence will not be gelled even inthe presence of water. Nevertheless, however, it is preferable todehydrate/dry the composition, when it is required to have storagestability for extended periods.

The preferable dehydration/drying method is drying under heating for thesolid, e.g., powdery, composition, and dehydration under a vacuum or inthe presence of synthetic zeolite, activated alumina or silica gel forthe liquid composition. Moreover, it maybe dehydrated in the presence ofa small quantity of an isocyanate compound, where the isocyanate groupreacts with water.

The composition will have still improved storage stability, when treatedfor dehydration/drying and incorporated with a lower alcohol, e.g.,methanol or ethanol; or alkoxysilane compound, e.g., n-propyltrimethoxysilane, vinyl methyldimethoxysilane,γ-mercaptopropylmethyldimethoxysilane,γ-mercaptopropylmethyldiethoxysilane orγ-glycidoxypropyltrimethoxysilane.

Curable Composition (4) and its Uses

The curable composition (4) of the present invention contains thecurable composition with the hydrolyzable silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber as thecomponent (A1), as described earlier. More concretely, it contains (a)the organic polymer (Z) and (b) the organosilicon compound (B4). It canbe suitably used for electric/electronic device members, transportationmachines, and civil engineering/construction, medical and leisure areas.

The curable composition (4) of the present invention can be used assealants, potting agents, coating materials or adhesives forelectric/electronic device members, transportation machines, and civilengineering/construction and leisure areas.

In other words, the present invention provides sealants, potting agents,coating materials and adhesives, composed of the curable composition,comprising (a) the organic polymer (Z) and (b) the organosiliconcompound (B4).

Rubber Composition Curable at Normal Temperature (5)

The rubber composition curable at normal temperature (5) of the presentinvention contains the silyl-containing ethylene/α-olefin/non-conjugatedpolyene random copolymer rubber (A1), a silane compound (B5), and, asrequired, a curing catalyst.

Silane Compound (B5)

The silane compound (B5) for the present invention is represented by oneof the following general formulae [VII-1] to [VII-6]:

wherein, R⁴ is a hydrocarbon group selected from the group consisting ofalkyl, aryl and aralkyl group of 1 to 10 carbon atoms;

-   -   X is a halogen or a group selected from the group consisting of        hydroxy, alkoxyl, acyloxy, aminoxy, phenoxy, thioalkoxy, amino,        ketoxymate and alkenyloxy group;    -   R⁵ is an alkylene or arylene group of 8 to 200 carbon atoms;    -   R⁶ is a monovalent alkyl group of 8 to 200 carbon atoms; and    -   “n” is an integer of 0 to 2.

The silane compound represented by the general formula [VII-1] or[VII-2] can be synthesized through hydrosilylation by reacting apolyolefin compound of a molecular weight of 100 to 3,000 having anallyl group at one or both terminals with the hydrosilane compoundrepresented by the following general formula:

wherein, R⁴ is a monovalent hydrocarbon group selected from the groupconsisting of alkyl, aryl and aralkyl group of 1 to 10 carbon atoms;

-   -   X is a halogen or a group selected from the group consisting of        hydroxy, alkoxyl, acyloxy, aminoxy, phenoxy, thioalkoxy, amino,        ketoxymate, alkenyloxy; and    -   “n” is an integer of 0 to 2.

The silane compound represented by the general formula [VII-3] or[VII-4] can be synthesized by the Williamson's ether synthesis methodfollowed by hydrosilylation, wherein a polyolefin compound having amolecular weight of 100 to 3,000 with hydroxyl group at one or bothterminals is provided with allyl group at one or both terminals in thefirst step, and the product is hydrosilylated with the above-describedhydrosilane compound in the second step.

The silane compound represented by the general formula [VII-5] or[VII-6] can be synthesized by, e.g., sealing a polyolefin compoundhaving a molecular weight of 100 to 3,000 with hydroxyl group at one orboth terminals with an isocyanate silane.

The hydrosilylation between the allyl group and hydrosilane compoundquantitatively proceeds at 50 to 150° C. for 1 to 4 hours in thepresence of a catalyst of Group 8 transition metal complex selected fromthe group consisting of platinum, rhodium, cobalt, palladium and nickel.

The reaction between the hydroxyl group and isocyanate silane canproceed in the presence or absence of a catalyst. However, a catalystmay be used, when the addition reaction is to be accelerated. Thecatalysts useful for the above purpose include organotin compounds,e.g., dibutyltin dilaurate and tinoctylate, and tertiary aminecompounds, e.g., dimethyl benzylamine and triethylamine. The reactionproceeds at 50 to 150° C., and is traced by the NCO absorption at 2270cm⁻¹ in the far-infrared absorption spectral pattern.

The concrete examples of the polyolefin compounds with allyl group atone or both terminals include 1-octene, 1-decene, 1-tetradecene,1-hexadecene, 1-octadecene, 1,7-octadiene, 1,9-decadiene and1,13-tetradecadiene.

The concrete examples of the polyolefin compounds with hydroxyl group atone or both terminals include 1-octanol, 1-decanol, 1-tetradecanol,1-hexadecanol, 1-octadecanol, 1,8-octanediol, 1,10-decanediol,1,14-tetradecanediol, 1,16-hexadecanediol, 1,18-octadecanediol,polyolefinpolyol (Polytail-HA, <M-1000>®, Polytail HA®, MitubishiChemical Corporation), and polybutadiene glycol and hydrogenatedpolybutadiene glycol (NISSO-PB G-1000®, NISSO-PB G-2000®, NISSO-PBGI-1000®, and NISSO-PB GI-2000®, Nippon Soda).

The concrete examples of the hydrosilane compounds include

-   -   halogenated silanes, e.g., trichlorosilane,        methyldichlorosilane, dimethylchlorosilane and        phenyldichlorosilane;    -   alkoxysilanes, e.g., trimethoxysilane, triethoxysilane,        methyldimethoxysilane, methyldiethoxysilane and        phenyldimethoxysilane;    -   acyloxysilanes, e.g., triacetoxysilane, methyldiacetoxysilane        and phenyldiacetoxysilane;    -   dimethylethylmethyloximesilane; and    -   triaminoxysilane, methyldiaminoxysilane and methyldiaminosilane.

The concrete examples of the isocyanate silane include γ-isocyanate,propyl trimethoxysilane, γ-isocyanate propyl triethoxysilane,γ-isocyanate propyl methyldimethoxysilane.

Curing Catalyst (C)

The concrete examples of the curing catalysts (C), which may be used forthe present invention, as required, include:

-   -   organotin compounds, e.g., dibutyl tin dilaurate, dibutyl tin        maleate, dioctyl tin laurate, dioctyl tin maleate and tin        octylate;    -   phosphoric acid and phosphate ester, e.g., phosphoric acid,        monomethyl phosphate, monoethyl phosphate, monobutyl phosphate,        monooctyl phosphate, monodecyl phosphate, dimethyl phosphate,        diethyl phosphate, dibutyl phosphate, dioctyl phosphate and        didecyl phosphate;    -   propylene oxide, butylene oxide, cyclohexene oxide, glycidyl        methacrylate, glycidol, allyl glycidyl ether,        γ-glycidoxypropyltrimethoxysilane,        γ-glycidoxypropyltriethoxysilane,        γ-glycidoxypropylmethyldimethoxysilane,

products of the addition reactions between an epoxy compound andphosphoric acid or mono acidic phosphate ester, e.g., CarduraE® (YukaShell Epoxy), and Epikote 828®and Epikote 1001® (Yuka Shell Epoxy);

-   -   mono[β-hydroxyethyl methacrylate] acid phosphate (KAYAMER PM-1®,        KAYAMER PM-2® and KAYAMER PM-21® (NIPPON KAYAKU), and copolymer        having a number-average molecular weight of 1,000 to 30,000 and        acidic phosphate ester group, produced by copolymerization of a        compound simultaneously having an acidic phosphate ester group        and polymerizable double bond in the molecule (e.g., product of        the reaction between glycidyl methacrylate and a phosphate) with        a vinyl monomer;    -   alkyl titanate;    -   organoaluminum;    -   acidic compounds, e.g., maleic acid and paratoluenesulfonic        acid;    -   amines, e.g., hexylamine, di-2-ethylhexylamine,        N,N-dimethyldodecylamine and dodecylamine; and    -   alkaline compounds, e.g., sodium hydroxide and potassium        hydroxide.

The reaction can proceed in the absence of the curing catalyst (C).However, the above catalysts may be used either individually or incombination, when the curing reaction is to be accelerated.

Compositional Ratio

The mixing ratio of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1),silane compound (B5) and curing catalyst (C) is preferably (A)/(B)/(C)of 100/0.1 to 100/0 to 20 by weight, more preferably 100/0.5 to 20/0.01to 10.

The silane compound (B5) cannot exhibit the effect of improving adhesionat a content below 0.1 parts by weight per 100 parts by weight of thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1), and may cause troubles, e.g., deterioratedcompatibility with the copolymer rubber (A1) and coating film becomingfragile, at above 100 parts by weight. Therefore, its content beyond theabove range is undesirable.

The mechanisms involved in the effect of the silane compound (B5) havinga long polyolefin chain to improve adhesion are not fully understood,but it conceivably results from incorporation of the compound (B5) ofrelatively low molecular weight into the network structure.

The effects of the silane compound (B5) are not limited to improvingadhesion to melamine alkyd or melamine acrylic resin, but to improvinghardness, resistance to solvents and pollution prevention of the rubbercomposition (5) of the present invention curable at normal temperature.These effects are particularly noted for improving hardness andresistance to solvents with the silane compound (B5) having 2hydrolyzable silyl groups in the molecule, and for improving pollutionprevention with the silane compound (B5) having one hydrolyzable silylgroup in the molecule.

Other Components

The rubber composition (5) of the present invention curable at normaltemperature may be incorporated with a dehydrator, although notessential. It may be incorporated, however, in order to keep the rubbercomposition (5) stable for extended periods or serviceable over repeatedcycles of use without causing problems.

The concrete examples of the dehydrators useful for the presentinvention include hydrolyzable ester compounds, e.g., methylorthoformate, ethyl orthoformate, methyl orthoacetate, ethylorthoacetate, methyltrimethoxysilane,γ-methacryloxypropyltrimethoxysilane, vinyl trimethoxysilane, methylsilicate and ethyl silicate.

The hydrolyzable ester compound may be added to the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1),while it is being produced or after it is produced.

The rubber composition (5) of the present invention curable at normaltemperature may be further incorporated with various additives, e.g.,anti-settling agent and leveling agent; cellulose, , e.g.,nitrocellulose and cellulose acetate butyrate; resin, e.g., alkyd,acrylic, vinyl chloride, chlorinated propylene, chlorinated rubber andpolyvinyl butyral rubber; adhesion improver; property adjuster; storagestability improver; plasticizer; filler; aging inhibitor; ultravioletray absorber; metal deactivator; ozone-caused aging inhibitor; lightstabilizer; amine-based radical chaining inhibitor; phosphorus-basedperoxide decomposer; lubricant; pigment; and foaming agent, withinlimits not detrimental to the object of the present invention.

For the adhesion improvers, the commonly used adhesives, silane couplingagents (e.g., aminosilane and epoxysilane compounds) and others may beused. The concrete examples of the adhesion improvers include phenolresin, epoxy resin, γ-aminopropyl trimethoxy silane,N-(β-aminoethyl)aminopropyl methyldimethoxy silane, coumarone/indeneresin, rosin ester resin, terpene/phenol resin, α-methyl styrene/vinyltoluene copolymer, polyethylmethyl styrene, alkyl titanate, and aromaticpolyisocyanate. The adhesion improver is incorporated preferably atabout 1 to 50 parts by weight per 100 parts by weight of thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1), more preferably 5 to 30 parts by weight.

The storage stability improvers useful for the present invention includeesters of ortho-organic acids. The storage stability improver isincorporated preferably at about 0.5 to 20 parts by weight per 100 partsby weight of the silyl-containing ethylene/α-olefin/non-conjugatedpolyene random copolymer rubber (A1), more preferably 1 to 10 parts byweight.

The plasticizer useful for the present invention is also not limited,and any commonly used one may be used. Preferably, it should becompatible with each component for the rubber composition (5) of thepresent invention curable at normal temperature.

The concrete examples of these plasticizers include:

-   -   hydrocarbon-based compounds, e.g., polybutene, hydrogenated        polybutene, ethylene/α-olefin co-oligomer, α-methyl styrene        oligomer, biphenyl, triphenyl, triaryl dimethane, alkylene        triphenyl, liquid polybutadiene, hydrogenated liquid        polybutadiene, alkyl diphenyl, partially hydrogenated        ter-phenyl, paraffin oil, naphthene oil and atactic        polypropylene;    -   parafin chlorides;    -   phthalate esters, e.g., those of dibutyl phthalate, diheptyl        phthalate, di(2-ethylhexyl) phthalate, butyl benzyl phthalate        and butyl phthalyl butyl glycolate;    -   non-aromatic, dibasic acid esters, e.g., those of dioctyl        adipate and dioctyl cebacate;    -   esters of polyalkylene glycol, e.g., those of diethylene glycol        benzoate and triethylene glycol dibenzoate; and    -   phosphate esters, e.g., those of tricresyl phosphate and        tributyl phosphate.

Of these, saturated hydrocarbon-based compounds are more preferable.They may be used either individually or in combination.

Of the above-described compounds, the hydrocarbon-based compounds freeof unsaturated group, e.g., hydrogenated polybutene, hydrogenated liquidpolybutadiene, paraffin oil, naphthene oil and atactic polypropylene,are more preferable for various reasons; e.g., high compatibility witheach component for the rubber composition of the present invention,limited effects on curing speed of the rubber composition, goodresistance to weather of the cured product, and cheapness.

The plasticizer may be used in place of the solvent during the processof introducing a hydrolyzable silyl group into the above-describedethylene/α-olefin/non-conjugated polyene random copolymer rubber (A₀),for the purposes of, e.g., adjusting reaction temperature and viscosityof the reaction system.

The plasticizer is incorporated preferably at about 10 to 500 parts byweight per 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1),more preferably about 20 to 300 parts by weight.

The concrete examples of the fillers include wood powder, pulp, cottonchips, asbestos, glass fibers, carbon fibers, mica, walnut shell powder,graphite, diatomaceous earth, white clay, fumed silica, settling silica,silicic anhydride, carbon black, calcium carbonate, clay, talc, titaniumoxide, magnesium carbonate, quartz, fine aluminum powder, flint powder,and zinc powder. Of these, more preferable ones are thixotropic fillers,e.g., settling silica, fumed silica and carbon black; and calciumcarbonate, titanium oxide and talc. The filler, when used, isincorporated preferably at about 10 to 500 parts by weight per 100 partsby weight of the silyl-containing ethylene/α-olefin/non-conjugatedpolyene random copolymer rubber (A1), more preferably about 20 to 300parts by weight.

The aging inhibitors useful for the present invention include commonlyused known sulfur-based ones, radical inhibitors and ultraviolet rayabsorbers.

The sulfur-based aging inhibitors useful for the present inventioninclude mercaptans, salts thereof, sulfides including sulfidecarboxylate esters and hindered phenol-based sulfides, polysulfides,dithiocarboxylates, thioureas, thiophosphates, sulfonium compounds,thioaldehydes, thioketones, mercaptals, mercaptols, monothio acids,polythio acids, thioamides, and sulfoxides.

More concretely, the sulfur-based aging inhibitors include:

-   -   mercaptans, e.g., 2-mercaptobenzothiazole;    -   salts of mercaptans, e.g., zinc salt of 2-mercaptobenzothiazole;    -   sulfides, e.g., 4,4′-thio-bis(3-methyl-6-t-butyl phenol),        4,4′-thio-bis(2-methyl-6-t-butyl phenol),        2,2′-thio-bis(4-methyl-6-t-butyl phenol),        bis(3-methyl-4-hydroxy-5-t-butylbenzyl) sulfide, terephthaloyl        di(2,6-dimethyl-4-t-butyl-3-hydroxybenzyl) sulfide,        phenothiazine, 2,2′-thio-bis (4-octyl phenol) nickel, dilauryl        thiodipropionate, distearyl thiodipropionate, dimyristyl        thiodipropionate, ditridecyl thiodipropionate,        distearylβ,β′-thiodibutyrate, lauryl-stearylthiodipropionate and        2,2-thio[diethyl-bis-3-(3,5-di-t-butyl-4-hydroxy        phenol)propionate];    -   polysulfides, e.g., 2-benzothiazole disulfide;    -   dithiocarboxylates, e.g., zincdibutyldithiocarbamate, zinc        diethyldithiocarbamate, nickel dibutyldithiocarbamate, zinc        di-n-butyldithiocarbamate, dibutyl ammonium        dibutyldithiocarbamate, zinc ethyl-phenyl-dithiocarbamate and        zinc dimethyldithiocarbamate;    -   thioureas, e.g., 1-butyl-3-oxy-diethylene-2-thiourea,        di-o-tolyl-thiourea and ethylene thiourea; and    -   thiophosphates, e.g., trilauryltrithiophosphate.

The above-described sulfur-based aging inhibitor preventsdecomposition/aging of the main chain under heating much moreefficiently than the other types for the curable rubber composition ofthe present invention, controlling the problems, e.g., residual surfacetackiness.

The radical inhibitors useful for the present invention includephenol-based ones, e.g., 2,2-methylene-bis(4-methyl-6-t-butyl phenol)and tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propio nate]methane; and amine-based ones, e.g., phenyl-β-naphthylamine,α-naphthylamine, N,N′-sec-butyl-p-phenylenediamine, phenothiazine andN,N′-diphenyl-p-phenylenediamine.

The ultraviolet ray absorbers useful for the present invention include2-(2′-hydroxy-3′,5′-di-t-butylphenyl) benzotriazole andbis(2,2,6,6-tetramethyl-4-piperidine) cebacate.

The aging inhibitor is incorporated at about 0.1 to 20 parts by weightper 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1),preferably 1 to 10 parts by weight.

Rubber Composition Curable at Normal Temperature (5) and its Uses

The rubber composition (5) of the present invention curable at normaltemperature contains the curable composition with the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber as thecomponent (A1). More concretely, it contains the organic polymer (Z),the silane compound (B5), and, as required, the curing catalyst (C). Itcan be suitably used for electric/electronic device members,transportation machines, and civil engineering/construction, medical andleisure areas, as described earlier.

The rubber composition (5) of the present invention curable at normaltemperature can be used as sealants, potting agents, coating materialsor adhesives for electric/electronic device members, transportationmachines, and civil engineering/construction, medical and leisure areas.

Curable Rubber Composition (6)

The curable rubber composition (6) of the present invention contains thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1), and specific amines (D), a specific silanecoupling agent (B6) and a specific resin (E) as the active ingredients.

Amines (D)

The amines (D) useful for the present invention are selected from thegroup consisting of aliphatic amines, alicyclic amines, modifiedcycloaliphatic polyamines and ethanolamines.

The concrete examples of the aliphatic amines useful for the presentinvention include triethylamine, ethylenediamine, hexanediamine,diethylenetriamine, triethylenetetramine and tetraethylenepentamine.

The concrete examples of the alicyclic amines useful for the presentinvention include piperidine and piperazine.

The concrete examples of the modified cycloaliphatic polyamines usefulfor the present invention include those used as hardening agents forepoxy resin.

The concrete examples of the ethanolamines useful for the presentinvention include monoethanolamine, diethanolamine and triethanolamine.

These amines maybe used either individually or in combination.

The amines are incorporated normally at 30 parts by weight or less butmore than 0 parts per 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1),more preferably 0.1 to 5 parts by weight.

Silane Coupling Agents (B6)

The silane coupling agent (B6) useful for the present invention isrepresented by the following general formulaY₃(Si)Zwherein Y is an alkoxyl group; and Z is an alkyl group containing afunctional group selected from the group consisting of an amino groupwhich may be substituted with an aminoalkyl group or not, and mercaptogroup.

The concrete examples of the silane coupling agents (B6) represented bythe above-described general formula includeγ-aminopropyltriethoxysilane,N-β-(aminoethyl)-γaminopropyltriethoxysilane,γ-mercaptopropyltriethoxysilane, γ-aminopropyltrimethoxysilane,N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane,γ-mercaptopropyltrimethoxysilane.

The silane coupling agent (B6) is incorporated normally at 10 parts byweight or less but more than 0 parts per 100 parts by weight of thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1), more preferably 0.1 to 5 parts by weight.

Resins (E)

The resins (E) useful for the present invention include a knownlacquer-based, acrylic lacquer-based, acrylic resin-based, thermosettingacrylic, alkyd, melamine and epoxy paint, and organopolysiloxane.

For the present invention, an adequate quantity of the resin (E) ismixed with the silyl-containing ethylene/α-olefin/non-conjugated polyenerandom copolymer rubber (A1), the amines (D) and the silane couplingagent (B6)

Content of the resin (E) is not limited, but it is recommended to beincorporated normally at 0.1 to 1,000 parts by weight, including thesolvent when the resin (E) is dissolved therein, per 100 parts by weightof the silyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1), preferably 1 to 500 parts by weight.

Curable Rubber Composition (6)

The curable rubber composition (6) of the present invention is composedof the silyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1)! amines (D), a silane coupling agent (B6) and aresin (E) as the active ingredients, as described earlier.

The curable rubber composition (6) of the present invention maybeincorporated, as required, with various additives, e.g., adhesionimprover, property adjuster, storage stability improver, plasticizer,filler, aging inhibitor, ultraviolet ray absorber, metal deactivator,ozone-induced aging inhibitor, light stabilizer, amine-based radicalchaining inhibitor, phosphorus-based peroxide decomposer, lubricant,pigment and foaming agent, within limits not detrimental to the objectof the present invention.

The adhesion improvers useful for the present invention include silanecoupling agents, e.g., commonly used adhesives and aminosilanecompounds; and others. The concrete examples of these adhesion improversinclude phenolic resin, epoxy resin, γ-aminopropyl trimethoxysilane,N-(β-aminoethyl)aminopropyl methyldimethoxysilane, coumarone/indeneresin, rosin ester resin, terpene/phenol resin, α-methyl styrene/vinyltoluene copolymer, polyethylmethyl styrene, alkyl titanate, and aromaticpolyisocyanate. The adhesion improver, when used, is incorporatedpreferably at about 1 to 50 parts by weight per 100 parts by weight ofthe silyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1), more preferably about 5 to 30 parts by weight.

The storage stability improvers useful for the present invention includeesters of ortho-organic acids, e.g., alkyl ortho-formate.

The storage stability improver, when used, is incorporated preferably atabout 0.5 to 20 parts by weight per 100 parts by weight of thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1), more preferably about 1 to 10 parts by weight.

The plasticizer useful for the present invention is also not limited,and any commonly used one may be used. Preferably, it should becompatible with each component for the rubber composition (6) of thepresent invention.

The concrete examples of these plasticizers include:

hydrocarbon-based compounds, e.g., polybutene, hydrogenated polybutene,ethylene/α-olefin co-oligomer, α-methyl styrene oligomer, biphenyl,triphenyl, triaryl dimethane, alkylene triphenyl, liquid polybutadiene,hydrogenated liquid polybutadiene, alkyl diphenyl, partiallyhydrogenated ter-phenyl, paraffin oil, naphthene oil and atacticpolypropylene;

parafin chlorides;

phthalate esters, e.g., those of dibutyl phthalate, diheptyl phthalate,di(2-ethylhexyl) phthalate, butyl benzyl phthalate and butyl phthalylbutyl glycolate;

non-aromatic, dibasic acid esters, e.g., those of dioctyl adipate anddioctyl cebacate;

esters of polyalkylene glycol, e.g., those of diethylene glycol benzoateand triethylene glycol dibenzoate; and

phosphate esters, e.g., those of tricresyl phosphate and tributylphosphate. Of these, saturated hydrocarbon-based compounds are morepreferable. They may be used either individually or in combination.

Of these, the hydrocarbon-based compounds free of unsaturated group(e.g., hydrogenated polybutene, hydrogenated liquid polybutadiene,paraffin oil, naphthene oil and atactic polypropylene) are morepreferable, because they are well compatible with various components forthe rubber composition (6) of the present invention, affecting curingspeed of the rubber composition to only a limited extent, giving thecured product of high resistance to weather, and inexpensive.

The above plasticizer may replace the solvent used when a hydrolyzablesilyl group is introduced into the above-describedethylene/α-olefin/non-conjugated polyene random copolymer rubber (A₀),in order to adjust reaction temperature and viscosity of the reactionsystem.

The plasticizer, when used, is incorporated preferably at about 10 to500 parts by weight per 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1),more preferably about 20 to 300 parts by weight.

The concrete examples of the fillers include wood powder, pulp, cottonchips, asbestos, glass fibers, carbon fibers, mica, walnut shell powder,graphite, diatomaceous earth, white clay, fumed silica, settling silica,silicic anhydride, carbon black, calcium carbonate, clay, talc, titaniumoxide, magnesium carbonate, quartz, fine aluminum powder, flint powder,and zinc powder. Of these, more preferable ones are thixotropic fillers,e.g., settling silica, fumed silica and carbon black; and calciumcarbonate, titanium oxide and talc. The filler, when used, isincorporated preferably at about 10 to 500 parts by weight per 100 partsby weight of the silyl-containing ethylene/α-olefin/non-conjugatedpolyene random copolymer rubber (A1), more preferably about 20 to 300parts by weight.

The aging inhibitors useful for the present invention include commonlyused known ones, e.g., sulfur-based ones, radical inhibitors andultraviolet ray absorbers.

The sulfur-based aging inhibitors useful for the present inventioninclude mercaptans, salts thereof, sulfides including sulfidecarboxylate esters and hindered phenol-based sulfides, polysulfides,dithiocarboxylates, thioureas, thiophosphates, sulfonium compounds,thioaldehydes, thioketones, mercaptals, mercaptols, monothio acids,polythio acids, thioamides, and sulfoxides.

The concrete examples of the sulfur-based aging inhibitors useful forthe present invention include:

mercaptans, e.g., 2-mercaptobenzothiazole;

salts of mercaptans, e.g., zinc salt of 2-mercaptobenzothiazole;

sulfides, e.g., 4,4′-thio-bis(3-methyl-6-t-butyl phenol),4,4′-thio-bis(2-methyl-6-t-butyl phenol),2,2′-thio-bis(4-methyl-6-t-butyl phenol),bis(3-methyl-4-hydroxy-5-t-butylbenzyl) sulfide,terephthaloyldi(2,6-dimethyl-4-t-butyl-3-hydroxybenzyl) sulfide,phenothiazine, 2,2′-thio-bis (4-octyl phenol) nickel, dilaurylthiodipropionate, distearyl thiodipropionate, dimyristylthiodipropionate, ditridecyl thiodipropionate,distearylβ,β′-thiodibutyrate, lauryl-stearyl thiodipropionate and2,2-thio[diethyl-bis-3-(3,5-di-t-butyl-4-hydroxy phenol)propionate];

polysulfides, e.g., 2-benzothiazole disulfide;

dithiocarboxylates, e.g., zincdibutyldithiocarbamate, zincdiethyldithiocarbamate, nickel dibutyldithiocarbamate, zincdi-n-butyldithiocarbamate, dibutyl ammonium dibutyldithiocarbamate, zincethyl-phenyl-dithiocarbamate and zinc dimethyldithiocarbamate;

thioureas, e.g., 1-butyl-3-oxy-diethylene-2-thiourea,di-o-tolyl-thiourea and ethylene thiourea; and

thiophosphates, e.g., trilauryltrithiophosphate.

The above-described sulfur-based aging inhibitor preventsdecomposition/aging of the main chain under heating much moreefficiently than the other types for the curable rubber composition ofthe present invention, controlling the problems, e.g., residual surfacetackiness.

The radical inhibitors useful for the present invention includephenol-based ones, e.g., 2,2-methylene-bis(4-methyl-6-t-butyl phenol)and tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propio nate]methane; and amine-based ones, e.g., phenyl-β-naphthylamine,α-naphthylamine, N,N′-sec-butyl-p-phenylenediamine, phenothiazine andN,N′-diphenyl-p-phenylenediamine.

The ultraviolet ray absorbers useful for the present invention include2-(2′-hydroxy-3′,5′-di-t-butylphenyl) benzotriazole andbis(2,2,6,6-tetramethyl-4-piperidine) cebacate.

The aging inhibitor, when used, is incorporated preferably at about 0.1to 20 parts by weight per 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1),more preferably about 1 to 10 parts by weight.

Curable Rubber Composition (6) and its Uses

The curable rubber composition (6) of the present invention contains thecurable composition with the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber as thecomponent (A1). More concretely, it contains the organic polymer (Z),the amines (D), the silane coupling agent (B6) and resin (E) as theactive ingredients, the resin (E) being composed of a lacquer-based,acrylic lacquer-based, acrylic resin-based, thermosetting acrylic,alkyd, melamine or epoxy paint, or organopolysiloxane. It can besuitably used for electric/electronic device members, transportationmachines, and civil engineering/construction, medical and leisure areas,as described earlier.

The curable rubber composition (6) of the present invention can be usedas sealants, potting agents, coating materials or adhesives forelectric/electronic device members, transportation machines, and civilengineering/construction and leisure areas.

Curable Composition (7)

The curable composition (7) of the present invention contains (a) thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1) and (b) a silane-based compound substituted withamino group (B7).

The curable composition (7) of the present invention preferably contains(a) the silyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1), (b) the compound having a silanol group and/orthe compound which can react with moisture to form a compound having asilanol group in the molecule (B1), and the above-described silane-basedcompound substituted with amino group (B7),wherein the compound (B7) iscomposed of:

-   (c) a compound having a group containing silicon, to which 2    hydrolyzable groups are bonded, and amino group (B7-1), and-   (d) a compound having a group containing silicon, to which 3    hydrolyzable groups are bonded, and amino group (B7-2).

The curable composition (7) of the present invention exhibits excellentcharacteristics with respect to curing speed and resistance to weather,which are mainly derived from the ethylene/α-olefin/non-conjugatedpolyene random copolymer rubber (A1) containing the hydrolyzable silylgroup.

The curable composition (7) of the present invention is incorporated, asrequired, with a compound having a silanol group and/or a compound whichcan react with moisture to form a compound having a silanol group in themolecule (monovalent silanol-based compound) (B1).

The component (B1) is expected to bring the effect of decreasing modulusof the cured silyl-containing ethylene/α-olefin/non-conjugated polyenerandom copolymer rubber (A1). It is readily available, and has theexcellent characteristic in that it produces the above effect whenmerely incorporated in the ethylene/α-olefin/non-conjugated polyenerandom copolymer rubber containing the hydrolyzable silyl group (A1).

Silane-based Compound Containing Amino Group (B7)

The curable composition (7) of the present invention is incorporatedwith a silane-based compound containing amino group (B7), in combinationwith the ethylene/α-olefin/non-conjugated polyene random copolymerrubber containing the hydrolyzable silyl group (A1). Various types ofsilane-based compounds containing amino group may be used, individuallyor in combination. It is however preferable to simultaneously use thecompounds (B7-1) and (B7-2) described in detail below, wherein thecompound (B7-1) has a group containing silicon, to which 2 hydrolyzablegroups are bonded, and amino group(s) (bifunctional aminosilanecompound) and the compound (B7-2) has a group containing silicon, towhich 3 hydrolyzable groups are bonded, and amino group(s)(trifunctional aminosilane compound).

Bifunctional Aminosilane Compound (B7-1)

The group containing silicon to which 2 hydrolyzable groups are bondedin the bifunctional aminosilane compound (B7-1) for the presentinvention is represented by the following general formula:

wherein, R² is a monovalent organic group of 1 to 40 carbon atoms; andX′ is a hydrolyzable group.

The examples of the hydrolyzable groups include halogen and hydrogenatom, and alkoxyl, acyloxy, ketoxymate, amino, amide, aminoxy, mercaptoand alkenyloxy group. Alkoxyl group, e.g., methoxy or ethoxy, is morepreferable because of its mild hydrolyzability.

Amino group may be —NH₂ or substituted amino group, e.g., —NH₂ whosehydrogen atom is substituted with another group. The amino group isrepresented by the general formula —N(R⁴)₂, wherein R⁴ is hydrogen atomor a hydrocarbon group of 1 to 30 carbon atoms, which may be substitutedor not, and may be the same or different).

The concrete examples of the bifunctional aminosilane compounds (B7-1)include H₂NCH₂CH₂CH₂Si(CH₃)(OCH₃)₂, H₂NCH₂CH₂NHCH₂CH₂CH₂Si(CH₃)(HCH₃)₂,(CH₃)NHCH₂CH₂CH₂Si(CH₃)(OCH₃)₂, (C₂H₅)NHCH₂CH₂NHCH₂CH₂CH₂Si(CH₃)(OCH₃)₂,H₂NCH₂CH₂CH₂Si(CH₃)(OCOCH₃)₂, H₂NCH₂CH₂CH₂Si(CH₃)(ON═C(CH₃)(C₂H₅))₂ andH₂NCH₂CH₂CH₂Si(CH₃)(OC(CH₃)═CH₂)₂.

The bifunctional aminosilane compound (B7-1) is incorporated preferablyat 0.1 to 20 parts by weight per 100 parts by weight of thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1), more preferably 0.5 to 10 parts by weight. At thesame time, it is not desirable to incorporate the bifunctionalaminosilane compound (B7-1) at an excessive content relative to themonovalent silanol-based compound (B₁). The monovalent silanol-basedcompound (B1)/bifunctional aminosilane compound (B7-1) ratio ispreferably 1/0.01 to 1/5 by weight, more preferably 1/0.05 to 1/2 byweight.

Trifunctional Aminosilane Compound (B7-2)

The group containing silicon to which 3 hydrolyzable groups are bondedin the trifunctional aminosilane compound (B7-2) for the presentinvention is represented by the general formul a —SiX₃, wherein X is ahydrolyzable group. The amino group can be the same as that describedearlier.

The concrete examples of the trifunctional aminosilane compounds (B7-2)include H₂NCH₂CH₂CH₂Si(OCH₃)₃, H₂NCH₂CH₂NHCH₂CH₂CH₂Si(OCH₃)₃,(CH₃)NHCH₂CH₂CH₂Si(OCH₃)₃, (C₂H₅)NHCH₂CH₂NHCH₂CH₂CH₂Si(OCH₃)₃,H₂NCH₂CH₂CH₂Si(OCOCH₃)₃, H₂NCH₂CH₂CH₂Si(ON═C(CH₃)(C₂H₅))₃ andH₂NCH₂CH₂CH₂Si(OC(CH₃)═CH₂)₃.

The trifunctional amino silane compound (B7-2) is incorporatedpreferably at 0.01 to 5 parts by weight per 100 parts by weight of thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1), more preferably 0.05 to 3 parts by weight. At thesame time, it is not desirable to incorporate the trifunctionalaminosilane compound (B7-2) at an excessive content relative to themonovalent silanol-based compound (B1), because of increased modulus ofthe cured composition. The monovalent silanol-based compound(B1)/trifunctional aminosilane compound (B7-2) ratio is preferably1/0.01 to 1/0.75 by weight, more preferably 1/0.02 to 1/0.5 by weight.

Other Components

The curable composition (7) of the present invention may beincorporated, as required, with one or more additives, e.g., a curingpromoter, a plasticizer or a filler.

The curing promoters useful for the present invention include anorganotin compound, an acidic phosphate ester, a product by the reactionbetween an acidic phosphate ester and an amine, saturated or unsaturatedpolyvalent carboxylic acid or its anhydride, and organic titanatecompounds.

The organotin compounds useful for the present invention include dibutyltin dilaurate, dioctyl tin maleate, dibutyl tin phthalate, tin octylateand dibutyl tin methoxide.

The acidic phosphate esters useful for the present invention includethose containing the part represented by the following formula

for example, those represented by the following general formula:

wherein, “d” is 1 or 2; and R⁵ is an organic group. More concretely,they include the following compounds:

The organic titanate compound includes titanate esters, e.g., those oftetrabutyl titanate, tetraisopropyl titanate and triethanolaminetitanate.

The curing promoter, when used, is incorporated preferably at 0.1 to 10parts by weight per 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1).

The plasticizers useful for the present invention includelow-molecular-weight plasticizers, e.g., dioctyl phthalate,high-molecular-weight plasticizers, and high-viscosity plasticizers.

The concrete examples of the plasticizers useful for the presentinvention include phthalate esters, e.g., those of dibutyl phthalate,diheptyl phthalate, di(2-ethylhexyl) phthalate, butyl benzyl phthalateand butyl phthalyl butyl glycolate; non-aromatic, dibasic acid esters,e.g., those of dioctyl adipate and dioctyl cebacate; esters ofpolyalkylene glycol, e.g., those of diethylene glycol dibenzoate andtriethylene glycol dibenzoate; phosphate esters, e.g., those oftricresyl phosphate and tributyl phosphate; chlorinated paraffins; and

hydrocarbon-based oils, e.g., alkyl diphenyl, polybutene, hydrogenatedpolybutene, ethylene/α-olefin oligomer, α-methyl styrene oligomer,biphenyl, triphenyl, triaryl dimethane, alkylene triphenyl, liquidpolybutadiene, hydrogenated liquid polybutadiene, paraffin oil,naphthene oil, atactic polypropylene and partially hydrogenatedter-phenyl.

These plasticizers may be used either individually or in combination.The plasticizer may be incorporated, while the polymer is produced.

Of these, the hydrocarbon-based compounds free of unsaturated groups(e.g., hydrogenated polybutene, hydrogenated liquid polybutadiene,paraffin oil, naphthene oil and atactic polypropylene) are morepreferable, because they are well compatible with various components forthe curable composition (7) of the present invention, affecting curingspeed of the composition to only a limited extent, giving the curedproduct of high resistance to weather, and inexpensive.

The above plasticizer maybe selected in dependence on specific purposes,e.g., adjustment of characteristics and properties.

The plasticizer, when used, is incorporated preferably at about 1 to 400parts by weight per 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1),more preferably 1 to 150 parts, still more preferably 10 to 120 parts,particularly preferably 20 to 100 parts by weight.

The concrete examples of the fillers include wood powder, pulp, cottonchips, asbestos, glass fibers, carbon fibers, mica, walnut shell powder,rice hull powder, graphite, diatomaceous earth, white clay, fumedsilica, settling silica, silicic anhydride, carbon black, calciumcarbonate, clay, kaolin, talc, titanium oxide, magnesium carbonate,quartz powder, glass beads, fine aluminum powder, flint powder, and zincpowder. Of these, more preferable ones are thixotropic fillers, e.g.,settling silica, fumed silica and carbon black; and calcium carbonate,titanium oxide and talc. They may be used either individually or incombination.

The aging inhibitors useful for the present invention include commonlyused known ones, e.g., sulfur-based ones, radical inhibitors andultraviolet ray absorbers.

The sulfur-based aging inhibitors useful for the present inventioninclude mercaptans, salts thereof, sulfides including sulfidecarboxylate esters and hindered phenol-based sulfides, polysulfides,dithiocarboxylates, thioureas, thiophosphates, sulfonium compounds,thioaldehydes, thioketones, mercaptals, mercaptols, monothio acids,polythio acids, thioamides, and sulfoxides.

More concretely, the sulfur-based aging inhibitors include:

mercaptans, e.g., 2-mercaptobenzothiazole; salts of mercaptans, e.g.,zinc salt of 2-mercaptobenzothiazole; sulfides, e.g.,4,4′-thio-bis(3-methyl-6-t-butyl phenol),4,4′-thio-bis(2-methyl-6-t-butyl phenol),2,2′-thio-bis(4-methyl-6-t-butyl phenol),bis(3-methyl-4-hydroxy-5-t-butylbenzyl) sulfide, terephthaloyldi(2,6-dimethyl-4-t-butyl-3-hydroxybenzyl) sulfide, phenothiazine,2,2′-thio-bis (4-octyl phenol) nickel, dilauryl thiodipropionate,distearyl thiodipropionate, dimyristyl thiodipropionate, ditridecylthiodipropionate, distearylβ,β′-thiodibutyrate, lauryl-stearylthiodipropionate and 2,2-thio[diethyl-bis-3-(3,5-di-t-butyl-4-hydroxyphenol)propionate]; polysulfides, e.g., 2-benzothiazole disulfide;dithiocarboxylates, e.g., zinc dibutyldithiocarbamate, zincdiethyldithiocarbamate, nickel dibutyldithiocarbamate, zincdi-n-butyldithiocarbamate, dibutyl ammonium dibutyldithiocarbamate, zincethyl-phenyl-dithiocarbamate and zinc dimethyldithiocarbamate;thioureas, e.g., 1-butyl-3-oxy-diethylene-2-thiourea,di-o-tolyl-thiourea and ethylene thiourea; and

thiophosphates, e.g., trilauryltrithiophosphate.

The above-described sulfur-based aging inhibitor preventsdecomposition/aging of the main chain under heating much moreefficiently than the other types for the curable composition (7) of thepresent invention, controlling the problems, e.g., residual surfacetackiness.

The radical inhibitors useful for the present invention includephenol-based ones, e.g., 2,2-methylene-bis(4-methyl-6-t-butyl phenol)and tetrakis [methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane; and amine-based ones, e.g., phenyl-β-naphthylamine,α-naphthylamine, N,N′-sec-butyl-p-phenylenediamine, phenothiazine andN,N′-diphenyl-p-phenylenediamine.

The ultraviolet ray absorbers useful for the present invention include2-(2′-hydroxy-3′,5′-di-t-butylphenyl) benzotriazole andbis(2,2,6,6-tetramethyl-4-piperidine) cebacate.

The curable composition (7) of the present invention thus prepared isuseful for adhesives, tackifiers, paints, waterproof materials forcoating films, sealant compositions, shaping materials, casting rubbermaterials and foaming materials.

When used as a sealant for construction works, for example, thecomposition (7) of the present invention is incorporated with aninorganic filler, e.g., calcium carbonate, talc or kaolin, normally at10 to 300 parts by weight, and further with a pigment (e.g., titaniumoxide, carbon black), ultraviolet ray absorber or aging inhibitor(radical chaining inhibitor), as required, and kneaded sufficientlyuniformly by a kneader or paint roll. The composition is cured, whenapplied and exposed to moisture in air, into a rubber elastomer of goodcharacteristics.

Curable Composition (7) and its Uses

The curable composition (7) of the present invention contains thecurable composition with the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber as thecomponent (A1). More concretely, the curable composition (7), containing(a) the organic polymer (Z) and (b) the silane-based compoundsubstituted with amino group (B7) can be suitably used forelectric/electronic device members, transportation machines, and civilengineering/construction, medical and leisure areas, as describedearlier.

It is preferable, as described earlier, that the composition (7) iscomposed of:

-   (a) the organic polymer (Z),-   (b) the monovalent silanol-based compound (B1), and the    above-described silane-based compound substituted with amino group    (B7), which is composed of:-   (c) the bifunctional aminosilane compound (B7-1) and-   (d) the trifunctional aminosilane compound (B7-2).

The curable composition (7) of the present invention can be suitablyused as sealants, potting agents, coating materials or adhesives forelectric/electronic device members, transportation machines, and civilengineering/construction, medical and leisure areas.

In other words, the present invention can provide sealants, pottingagents, coating materials and adhesives, composed of the curablecomposition containing the organic polymer (Z) and silane-based compoundsubstituted with amino group (B7).

It is preferable, as described earlier, that each of the sealants,potting agents, coating materials and adhesives is composed of:

-   (a) the organic polymer (Z),-   (b) the monovalent silanol-based compound (B1), and the    above-described silane-based compound substituted with amino group    (B7), which is composed of:-   (c) the bifunctional aminosilane compound (B7-1) and-   (d) the trifunctional aminosilane compound (B7-2).

Curable Composition (8)

The curable composition (8) of the present invention contains thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1), and a filler (F), a plasticizer (G), a curingcatalyst (H) and an organocarboxylate compound (B8).

The curable composition (8) of the present invention exhibits excellentcharacteristics with respect to curing speed and resistance to weather,which is mainly derived from the ethylene/α-olefin/non-conjugatedpolyene random copolymer rubber (A1) containing the hydrolyzable silylgroup.

Filler (F)

The filler (F) useful for the present invention is not limited. Theconcrete examples of the fillers include reinforcing fillers, e.g.,fumed silica, settling silica, silicic anhydride, silicic hydride andcarbon black; inorganic or organic fillers, e.g., calcium carbonate,magnesium carbonate, diatomaceous earth, fired clay, clay, talc,titanium oxide, bentonite, organic bentonite, ferric oxide, zinc oxide,activated zinc white, hydrogenated castor oil, PVC and polyolefin;fibrous fillers, e.g., asbestos and glass fibers or filaments; inorganicor organic balloons, e.g., those of silas, glass, saran and phenol.

They may be used either individually or in combination.

Plasticizer (G)

The plasticizer (G) useful for the present invention is not limited. Theconcrete examples of the plasticizers include phthalate esters, e.g.,those of dibutyl phthalate, diheptyl phthalate, di(2-ethylhexyl)phthalate, dioxtyl phthalate, butyl benzyl phthalate and butyl phthalylbutyl glycolate; non-aromatic, dibasic acid esters, e.g., those ofdioctyl adipate and dioctyl cebacate; esters of polyalkylene glycol,e.g., those of diethylene glycol dibenzoate and triethylene glycoldibenzoate; phosphate esters, e.g., those of tricresyl phosphate andtributyl phosphate; chlorinated paraffins; and hydrocarbon-based oils,e.g., alkyl diphenyl, polybutene, hydrogenated polybutene,ethylene/α-olefin oligomer, α-methyl styrene oligomer, biphenyl,triphenyl, triaryl dimethane, alkylene triphenyl, liquid polybutadiene,hydrogenated liquid polybutadiene, paraffin oil, naphthene oil, atacticpolypropylene and partially hydrogenated ter-phenyl.

These compounds may be used either individually or in combination. Theplasticizer may be incorporated, while the polymer is produced.

Of these, the hydrocarbon-based compounds are more preferable, becausethey are commonly used, low in cost and excellent in resistance toweather.

Curing Catalyst (H)

The curing catalyst (H) useful for the present invention is not limited.The concrete examples of the curing catalysts include silanol condensingcatalysts, such as: titanate esters, e.g., those of tetrabutyl titanateand tetrapropyl titanate; tin carbonates, e.g., dibutyl tin dilaurate,dibutyl tin maleate, dibutyl tin diacetate, tin octylate and tinnaphthenate; product of the reaction between dibutyl tin oxide and aphthalate ester; dibutyl tin acetylacetonate; organoaluminum compounds,e.g., aluminum trisacetylacetonate, aluminum trisethylacetoacetate anddiisopropoxy aluminum ethylacetoacetate; chelate compounds, e.g.,zirconium tetraacetylacetonate and titanium tetraacetylacetonate; leadoctylate; amine-based compounds, and salts of these compounds andcarboxylates, e.g., butylamine, octylamine, laurylamine, dibutylamine,monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine,triethylenetetramine, oleylamine, cyclohexylamine, benzylamine,diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine,diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine,N-methyl morpholine, 2-ethyl-4-methylimidazole and1,8-diazabicyclo(5,4,0) undecene-7 (DBU); low-molecular-weight polyamideresins produced by the reactions between excessive quantities ofpolyamines and polybasic acids; products of the reactions betweenexcessive quantities of polyamines and epoxy compounds; andamine-containing silane coupling agents, e.g., γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)aminopropyl methyldimethoxysilane. Thesilanol condensing catalysts useful for the present invention are notlimited to the above, and include the commonly used condensingcatalysts, acidic or basic. These catalysts may be used eitherindividually or in combination.

Of these curing catalysts, more preferable ones are titanium- andtin-based ones, viewed from availability and cost performance.

The curing condensing catalyst is incorporated preferably at about 0.1to 20 parts by weight per 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1),more preferably 1 to 10 parts by weight. The catalyst content below theabove-mentioned range is undesirable, because of insufficient curingspeed and insufficient extent of the curing reaction, and the contentbeyond the above range is also undesirable, because of local heating orfoaming occurring during the curing process to make it difficult toproduce the cured product of good properties.

Organocarboxylic Acid Compound (B8)

The organocarboxylic acid compounds (B8) useful for the presentinvention include aliphatic monocarboxylic, aliphatic dicarboxylic,aliphatic polycarboxylic, and aromatic carboxylic acids. The concreteexamples are described below for each type, although not limitedthereto.

(1)Aliphatic monocarboxylic acids:

-   (a) saturated aliphatic monocarboxylic acids, e.g., formic, acetic,    acetoacetic, ethylmethylacetic, propionic, butyric, isobutyric,    2-ethylbutyric, ethoxybutyric, valeric, isovaleric, hexanic,    2-ethylhexanic, octanic, decanic, undecanic, stearic, glyoxylic,    glycolic and gluconic acids;-   (b) olefinic monocarboxylic acids, e.g., acrylic, methacrylic,    angelic, crotonic, isocrotonic, 10-undecenic, elaidic, erucic and    oleic acids;-   (c) acetylenic monocarboxylic acids, e.g., propiolic acd;-   (d) diolefinic monocarboxylic acids, e.g., linolic and linoelaidic    acids;-   (e) highly unsaturated monocarboxylic acids, e.g., linolenic and    arachidonic acids; and-   (f) halogen-substituted monocarboxylic acids, e.g., chloroacetic,    2-chloroacrylic and chlorobenzoic acids;    (2) Aliphatic dicarboxylic acids:-   (a) saturated dicarboxylic acids, e.g., adipic, azelaic,    ethylmalonic, glutaric, oxalic, malonic, succinic and oxydiacetic    acids; and-   (b) unsaturated dicarboxylic acids, e.g., maleic, fumaric, acetylene    dicarboxylic and itaconic acids;    (3) Aliphatic polycarboxylic acids:-   (a) tricarboxylic acids, e.g., aconitic, citric and isocitric acids    (4) Aromatic carboxylic acids:-   (a) aromatic monocarboxylic acids, e.g., benzoic, 9-anthracene    carboxylic, atrolactic, anisic, isopropyl benzoic, salicylic and    toluylic acids; and-   (b) aromatic polycarboxylic acids, e.g., phthalic, isophthalic,    terephthalic, carboxyphenylacetic and pyromellitic acids    (5) Others

Amino acids, e.g., alanine, leucine, threonine, aspartic acid, glutamicacid, arginine, cysteine, methionine, phenylalanine, tryptophan andhistidine

Any compound may be used for the organocarboxylic acid (B8) for thepresent invention, so long as it has at least one carboxyl group. Thesecompounds may be used either indvidually or in combination. Of theabove-described compounds, aliphatic monocarboxylic compounds are morepreferable, those of 2 to 30 carbon atoms being still more preferable.

Content of the organocarboxylic acid (B8) can be set depending onpurposes, e.g., improvement of curing speed or of curing delay after thecomposition is stored. It is however incorporated normally at 0.01 to 10parts by weight per 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1),preferably 0.1 to 5 parts by weight, viewed from the balance betweenimprovement effects and cost.

Other Components

The curable composition (8) of the present invention may be adequatelyincorporated, as required, with various additives, e.g., dehydrator,tackifier, property adjuster, storage stability improver, aginginhibitor, ultraviolet ray absorber, metal deactivator, ozone-inducedaging inhibitor, light stabilizer, amine-based radical chaininginhibitor, phosphorus-based peroxide decomposer, lubricant, pigment andfoaming agent.

The dehydrators useful for the present invention include those reactivewith water, particularly preferably hydrolyzable silicon compounds. Thehydrolyzable silicon compound is a generic term for thelow-molecular-weight silicon compounds having a hydrolyzable functionalgroup reactive in the presence of moisture, normally preferably thosehaving a molecular weight of 300 or less. It may contain any functionalgroup, in addition to a hydrolyzable functional one. The hydrolyzablegroups include alkoxyl, acyloxy, ketoximate, amino, aminoxy, amide andalkenyloxy. The other functional groups include epoxy-, amino-, acrylic-and mercapto-containing groups.

The concrete examples of these compounds include

In addition to the dehydrator, an aminosilane compound may beincorporated as the tackifier agent and dehydrator.

The aminosilane compounds useful for the present invention includeamino-substituted alkoxysilanes and derivatives thereof. The concreteexamples of these compounds include the products by the reactions of anamino-substituted alkoxysilane or derivative thereof, e.g.,

with an epoxy silane, e.g.,

or the above described amino-substituted alkoxysilane with anacryloylsilane, e.g.,

The product of the reaction of an amino-substituted alkoxysilane withepoxy silane compound or with acryloylsilane compound can be easilyproduced by stirring the silane compound and amino-substitutedalkoxysilane, mixed in a molar ratio of 0.2 to 5, at room temperature to180° C. for 1 to 8 hours.

The amino-substituted alkoxysilane or derivative thereof is incorporatedpreferably at about 0.01 to 20 parts by weight per 100 parts by weightof the silyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1).

The adhesion improvers useful for the present invention include commonlyused adhesives and silane coupling agents, e.g., epoxysilane compoundsand aminosilane compounds; and others. The concrete examples of theseadhesion improvers include phenolic resins, epoxy resins, γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)aminopropyl methyldimethoxysilane,coumarone/indene resins, rosin ester resins, terpene/phenol resins,α-methyl styrene/vinyl toluene copolymers, polyethylmethyl styrenes,alkyl titanates, and aromatic polyisocyanates.

The storage stability improvers useful for the present invention includecompounds with silicon to which a hydrolyzable group is bonded andesters of ortho-organic acids. The concrete examples of the storagestability improvers include methyltrimethoxy silane, methyltriethoxysilane, tetramethoxy silane, ethyltrimethoxy silane, dimethyldiethoxysilane, trimethylisobutoxy silane, trimethyl (n-butoxy) silane,n-butyltrimethoxy silane, and methyl orthoformate.

The aging inhibitors useful for the present invention include commonlyused known ones, e.g., sulfur-based ones, radical inhibitors andultraviolet ray absorbers.

The sulfur-based aging inhibitors useful for the present inventioninclude mercaptans, salts thereof, sulfides including sulfidecarboxylate esters and hindered phenol-based sulfides, polysulfides,dithiocarboxylates, thioureas, thiophosphates, sulfonium compounds,thioaldehydes, thioketones, mercaptals, mercaptols, monothio acids,polythio acids, thioamides, and sulfoxides.

More concretely, the sulfur-based aging inhibitors include mercaptans,e.g., 2-mercaptobenzothiazole; salts of mercaptans, e.g., zinc salt of2-mercaptobenzothiazole; sulfides, e.g.,4,4′-thio-bis(3-methyl-6-t-butyl phenol),4,4′-thio-bis(2-methyl-6-t-butyl phenol),2,2′-thio-bis(4-methyl-6-t-butyl phenol),bis(3-methyl-4-hydroxy-5-t-butylbenzyl) sulfide,terephthaloyldi(2,6-dimethyl-4-t-butyl-3-hydroxybenzyl) sulfide,phenothiazine, 2,2′-thio-bis (4-octyl phenol) nickel, dilaurylthiodipropionate, distearyl thiodipropionate, dimyristylthiodipropionate, ditridecyl thiodipropionate,distearylβ,β′-thiodibutyrate, lauryl-stearyl thiodipropionate and2,2-thio[diethyl-bis-3(3,5-di-t-butyl-4-hydroxy phenol)propionate];polysulfides, e.g., 2-benzothiazole disulfide; dithiocarboxylates, e.g.,zinc dibutyldithiocarbamate, zinc diethyldithiocarbamate, nickeldibutyldithiocarbamate, zinc di-n-butyldithiocarbamate, dibutyl ammoniumdibutyldithiocarbamate, zinc ethyl-phenyl-dithiocarbamate and zincdimethyldithiocarbamate; thioureas, e.g.,1-butyl-3-oxy-diethylene-2-thiourea, di-o-tolyl-thiourea and ethylenethiourea; and thiophosphates, e.g., trilauryltrithiophosphate.

The above-described sulfur-based aging inhibitor preventsdecomposition/aging of the main chain under heating much moreefficiently than the other types for the composition of the presentinvention, controlling the problems, e.g., residual surface tackiness.

The radical inhibitors useful for the present invention includephenol-based ones, e.g., 2,2-methylene-bis(4-methyl-6-t-butyl phenol)and tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane; and amine-based ones, e.g., phenyl-β-naphthylamine,α-naphthylamine, N,N′-sec-butyl-p-phenylenediamine, phenothiazine andN,N′-diphenyl-p-phenylenediamine.

The ultraviolet ray absorbers useful for the present invention include2-(2′-hydroxy-3′,5′-di-t-butylphenyl) benzotriazole andbis(2,2,6,6-tetramethyl-4-piperidine) cebacate.

The method of producing the composition (8) of the present invention isnot limited. For example, the composition comprising the above-describedcomponents is kneaded at normal or elevated temperature by a mixer, rollor kneader, or mixing the components after being dissolved in a smallquantity of an adequate solvent. These components are incorporated in anadequate ratio, to produce a one-liquid or two-liquid type curablecomposition.

The curable composition (8) of the present invention forms thethree-dimensional network structures when exposed to moisture in air,transforming itself into the solid showing rubber-like elasticity.

Curable Composition (8) and its Uses

The curable composition (8) of the present invention contains thecurable composition with the hydrolyzable silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber as thecomponent (A1). More concretely, the curable composition (8) of thepresent invention contains (a) the organic polymer (Z), and a filler(F), plasticizer (G), curing catalyst (H) and organocarboxylate compound(B8). It can be suitably used for electric/electronic device members,transportation machines, and civil engineering/construction, medical andleisure areas, as described earlier.

The curable composition (8) of the present invention can be used assealants, potting agents, coating materials or adhesives forelectric/electronic device members, transportation machines, and civilengineering/construction, medical and leisure areas.

In other words, the present invention provides sealants, potting agents,coating materials and adhesives, composed of the curable composition,composed of the organic polymer (Z), and filler (F), plasticizer (G),curing catalyst (H) and organocarboxylate compound (B8).

The curable composition of the present invention (8) is particularlyuseful for an elastomer sealant for buildings, ships, automobiles androads. It is also useful for various types of sealant and adhesivecompositions, because it is adhesive to a wide range of bases, e.g.,formed shapes of glass, porcelain, lumber, metal s and resin in thepresence or absence of primer. Moreover, it is also useful fortackifiers, paints, waterproof materials for coating films, foodwrapping materials, shaping materials, casting rubber materials andfoaming materials.

Curable Rubber Composition (9)

The curable rubber composition (9) of the present invention contains thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1), alcohols (B9) and/or a hydrolyzable estercompound (I) (except a hydrolyzable organosilicon compound (B10).

Alcohols (B9)

Of the alcohols (B9) and/or hydrolyzable ester compounds (I) (except ahydrolyzable organosilicon compound (B10)) useful for the presentinvention, the concrete examples of the alcohols (B9) include metahnol,ethanol, 2-methoxyethanol, sec-butanol and tert-butanol. Preferably,these mentioned alcohols are used for the present invention.

The alcohols (B9) are incorporated preferably at 5 to 40 parts by weightper 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1),more preferably 7 to 30 parts, still more preferably 10 to 20 parts byweight. At below 5 parts, they may not sufficiently improve the storagestability of the curing composition as one of the objects of the presentinvention. At above 40 parts, on the other hand, a phenomenon known asbrushing may occur, which may make not only the composition itself butalso coating film thereof turbid white.

Hydrolyzable Ester Compound (I)

Of the alcohols (B9) and/or hydrolyzable ester compounds (I) (except ahydrolyzable organosilicon compound (B10)) useful for the presentinvention, the hydrolyzable ester compounds (I) are preferably alkylorthoformates. The concrete examples of alkyl orthoformates includemethyl orthoformate, ethyl orthoformate, propyl orthoformate, butylorthoformate and orthophenyl, of which methyl orthoformate and ethylorthoformate are more preferable. The hydrolyzable ester compounds (I)is incorporated preferably at 3 to 30 parts by weight per 100 parts byweight of the silyl-containing ethylene/α-olefin/non-conjugated polyenerandom copolymer rubber (A1), more preferably 5 to 20 parts, still morepreferably 10 to 20 parts by weight. At below 3 parts, it may notsufficiently improve the storage stability of the curing composition asone of the objects of the present invention. The upper limit of itscontent is not limited, but it is not highly economical to use it atabove 30 parts.

Hydrolyzable Organosilicon Compound (B10)

The hydrolyzable organosilicon compounds (B10) useful for the presentinvention include alkoxysilane compounds. The concrete examples of thesecompounds include trimethoxysilane, triethoxysilane,methyldiethoxysilane, methyldimethoxysilane, phenyldimethoxysilane,ethyldiethoxysilane, ethyldimethoxysilane, butyldiethoxysilane,butyldimethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane,butyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane,ethyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane,dimethyldiethoxysilane, dibutyldiethoxysilane, anddiphenyldiethoxysilane.

The hydrolyzable organosilicon compound (B10) is incorporated preferablyat 2 to 20 parts by weight per 100 parts by weight of thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1), more preferably 2 to 15 parts, still morepreferably 2 to 10 parts by weight. At below 2 parts, it may notsufficiently improve the storage stability of the curing composition asone of the objects of the present invention. At above 20 parts, on theother hand, the cured coating film may become fragile.

Curing Promotors

A curing promoter is not essential for curing the curable rubbercomposition of the present invention. The curing promoters useful forthe present invention, when used, include an alkyl titanate, metal saltof carboxylic acid (e.g., tin octylate and dibutyl tin laurate), aminesalt (e.g., dibutylamine-2-hexoate), and other acidic and basiccatalysts.

The curing promoter is incorporated preferably at 0.001 to 10 parts byweight per 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1).

Other Components

The curable rubber composition (9) of the present invention may beincorporated, as required, with one or more additives within limits notdetrimental to the object of the present invention. The additives usefulfor the present invention include adhesion improver, property adjuster,storage stability improver, plasticizer, filler; aging inhibitor,ultraviolet ray absorber, metal deactivator, ozone-caused aginginhibitor, light stabilizer, amine-based radical chaining inhibitor;phosphorus-based peroxide decomposer, lubricant, pigment, and foamingagent.

The adhesion improvers useful for the present invention include commonlyused adhesives and silane coupling agents, e.g., aminosilane compoundsand epoxy silane compounds; and others. The concrete examples of theseadhesion improvers include phenolic resins, epoxy resins, γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)aminopropyl methyldimethoxysilane,coumarone/indene resins, rosin ester resins, terpene/phenol resins,α-methyl styrene/vinyl toluene copolymers, polyethylmethyl styrenes,alkyl titanates, and aromatic polyisocyanates. The adhesion improver,when used, is incorporated preferably at about 1 to 50 parts by weightper 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1),more preferably 5 to 30 parts by weight.

The storage stability improvers useful for the present invention includeesters of ortho-organic acids (other than an alkyl orthoformate). Thestorage stability improver, when used, is incorporated preferably atabout 0.5 to 20 parts by weight per 100 parts by weight of thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1), more preferably 1 to 10 parts by weight.

The plasticizer useful for the present invention is also not limited,and any commonly used one may be used. Preferably, it should becompatible with each component for the rubber composition (9) of thepresent invention.

The concrete examples of these plasticizers include:

hydrocarbon-based compounds, e.g., polybutene, hydrogenated polybutene,ethylene/α-olefin oligomer, α-methyl styrene oligomer, biphenyl,triphenyl, triaryl dimethane, alkylene triphenyl, liquid polybutadiene,hydrogenated liquid polybutadiene, alkyl diphenyl, partiallyhydrogenated ter-phenyl, paraffin oil, naphthene oil and atacticpolypropylene;

parafin chlorides;

phthalate esters, e.g., those of dibutyl phthalate, diheptyl phthalate,di(2-ethylhexyl) phthalate, butyl benzyl phthalate and butyl phthalylbutyl glycolate;

non-aromatic, dibasic acid esters, e.g., those of dioctyl adipate anddioctyl cebacate;

esters of polyalkylene glycol, e.g., those of diethylene glycol benzoateand triethylene glycol dibenzoate; and

phosphate esters, e.g., those of tricresyl phosphate and tributylphosphate. Of these, saturated hydrocarbon-based compounds are morepreferable. They may be used either individually or in combination.

Of the above-described compounds, hydrocarbon-based compounds free ofunsaturated group, e.g., hydrogenated polybutene, hydrogenated liquidpolybutadiene, paraffin oil, naphthene oil and atactic polypropylene,are more preferable for various reasons, e.g., high compatibility witheach component for the rubber composition (9) of the present invention,limited effects on curing speed of the rubber composition, goodresistance to weather of the cured product, and cheapness.

The plasticizer may be used in place of the solvent during the processof introducing a hydrolyzable silyl group into the above-describedethylene/α-olefin/non-conjugated polyene random copolymer rubber (A₀),for the purposes of, e.g., adjusting reaction temperature and viscosityof the reaction system.

The plasticizer is incorporated preferably at about 10 to 500 parts byweight per 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1),more preferably about 20 to 300 parts.

The concrete examples of the fillers include wood powder, pulp, cottonchips, asbestos, glass fibers, carbon fibers, mica, walnut shell powder,graphite, diatomaceous earth, white clay, fumed silica, settling silica,silicic anhydride, carbon black, calcium carbonate, clay, talc, titaniumoxide, magnesium carbonate, quartz, fine aluminum powder, flint powder,and zinc powder. Of these, more preferable ones are thixotropic fillers,e.g., settling silica, fumed silica and carbon black; and calciumcarbonate, titanium oxide and talc. The filler, when used, isincorporated preferably at about 10 to 500 parts by weight per 100 partsby weight of the silyl-containing ethylene/α-olefin/non-conjugatedpolyene random copolymer rubber (A1), more preferably about 20 to 300parts by weight.

The aging inhibitors useful for the present invention include commonlyused known ones, e.g., sulfur-based ones, radical inhibitors andultraviolet ray absorbers.

The sulfur-based aging inhibitors useful for the present inventioninclude mercaptans, salts thereof, sulfides including sulfidecarboxylate esters and hindered phenol-based sulfides, polysulfides,dithiocarboxylates, thioureas, thiophosphates, sulfonium compounds,thioaldehydes, thioketones, mercaptals, mercaptols, monothio acids,polythio acids, thioamides, and sulfoxides.

More concretely, the sulfur-based aging inhibitors include:

mercaptans, e.g., 2-mercaptobenzothiazole;

salts of mercaptans, e.g., zinc salt of 2-mercaptobenzothiazole;

sulfides, e.g., 4,4′-thio-bis(3-methyl-6-t-butyl phenol),4,4′-thio-bis(2-methyl-6-t-butyl phenol),2,2′-thio-bis(4-methyl-6-t-butyl phenol),bis(3-methyl-4-hydroxy-5-t-butylbenzyl) sulfide, terephthaloyldi(2,6-dimethyl-4-t-butyl-3-hydroxybenzyl) sulfide, phenothiazine,2,2′-thio-bis (4-octyl phenol) nickel, dilauryl thiodipropionate,distearyl thiodipropionate, dimyristyl thiodipropionate, ditridecylthiodipropionate, distearylβ,β′-thiodibutyrate, lauryl-stearylthiodipropionate and 2,2-thio[diethyl-bis-3(3,5-di-t-butyl-4-hydroxyphenol)propionate];

polysulfides, e.g., 2-benzothiazole disulfide;

dithiocarboxylates, e.g., zinc dibutyldithiocarbamate, zincdiethyldithiocarbamate, nickel dibutyldithiocarbamate, zincdi-n-butyldithiocarbamate, dibutyl ammonium dibutyldithiocarbamate, zincethyl-phenyl-dithiocarbamate and zinc dimethyldithiocarbamate;

thioureas, e.g., 1-butyl-3-oxy-diethylene-2-thiourea,di-o-tolyl-thiourea and ethylene thiourea; and

thiophosphates, e.g., trilauryltrithiophosphate.

The above-described sulfur-based aging inhibitor preventsdecomposition/aging of the main chain under heating much moreefficiently than the other types for the curable rubber composition ofthe present invention, controlling the problems, e.g., residual surfacetackiness.

The radical inhibitors useful for the present invention includephenol-based ones, e.g., 2,2-methylene-bis(4-methyl-6-t-butyl phenol)and tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane; and amine-based ones, e.g., phenyl-β-naphthylamine,α-naphthylamine, N,N′-sec-butyl-p-phenylenediamine, phenothiazine andN,N′-diphenyl-p-phenylenediamine.

The ultraviolet ray absorbers useful for the present invention include2-(2′-hydroxy-3′,5′-di-t-butylphenyl) benzotriazole andbis(2,2,6,6-tetramethyl-4-piperidine) cebacate.

The aging inhibitor, when used, is incorporated at about 0.1 to 20 partsby weight per 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1),preferably 1 to 10 parts by weight.

Curable Rubber Composition (9)

The curable rubber composition (9) of the present invention contains, asdescribed earlier, the silyl-containing ethylene/α-olefin/non-conjugatedpolyene random copolymer rubber (A1), alcohols (B9) and/or ahydrolyzable ester (I), preferably an alkyl orthoformate, a hydrolyzableorganosilicon compound (B10), preferably an alkoxysilane compound, and,as required, a curable promoter.

Preparation of Curable Rubber Composition (9)

The method of preparing the curable rubber composition (9) is notlimited. One example is kneading the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1)together with the alcohols (B9) and/or hydrolyzable ester (I),hydrolyzable organosilicon compound (B10), and, as required, one or moreadditives, e.g., curing promoter, adhesion improver, property adjuster,storage stability improver, plasticizer, filler and pigment, touniformly disperse these components in the copolymer rubber. Thecomposition is kneaded at room temperature to 180° C. for 30 seconds to30 minutes by a planetary mixer, roll, kneader or intermix mixer.

The composition thus prepared is applicable to one-liquid type curablecomposition, to say nothing of two-liquid type. For the one-liquid type,it is essential to remove moisture from the composition when thecopolymer rubber (A1) is dispersed with the other components. It canwithstand storage for extended periods when kept in a closed condition,and quickly starts curing from the surface when exposed to theatmosphere. Moisture can be preferably removed from the compositionunder heating or by use of a mixer equipped with a pressure reducingdevice.

Curable Rubber Composition (9) and its Uses

The curable composition (9) of the present invention contains, asdescribed earlier, the curable composition with the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber as thecomponent (A1). More concretely, the curable composition (9) of thepresent invention contains the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1),alcohols (B9) and/or a hydrolyzable ester (I), a hydrolyzableorganosilicon compound (B10), and, as required, a curable promoter. Itcan be suitably used for electric/electronic device members,transportation machines, and civil engineering/construction, medical andleisure areas, as described earlier.

The curable rubber composition of the present invention (9) can besuitably used as sealants, potting agents, coating materials oradhesives for electric/electronic device members, transportationmachines, and civil engineering/construction, and leisure areas.

Curable Rubber Composition (10)

The curable rubber composition (10) of the present invention is a two-or multi-liquid type curable rubber composition composed of at least twoliquids, i.e., the major ingredient (I) containing the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1),and a curing agent (II) containing a silanol condensing (curing)catalyst (J) and water or a hydrate of a metallic salt (B11). The majoringredient (II) may be further incorporated with a silane couplingagent.

The curing agent (II) contains a silanol condensing catalyst (J) andwater or a hydrate of a metallic salt (B11).

Silanol Condensing (Curing) Catalyst (J)

The silanol condensing (curing) catalyst (J) as one of the componentsfor the hardening agent (II) for the present invention may be a knownone.

The concrete examples of the silanol condensing (curing) catalystsuseful for the present invention include:

titanate esters, e.g., those of tetrabutyl titanate and tetrapropyltitanate;

tin carbonates, e.g., dibutyl tin dilaurate, dibutyl tin diacetate,dibutyl tin diethylhexanoate, dibutyl tin dioctylate, dibutyl tindimethylmaleate, dibutyl tin diethylmaleate, dibutyl tin dibutylmaleate,dibutyl tin diisooctylmaleate, dibutyl tin ditridecylmaleate, dibutyltin dibenzylmaleate, dibutyl tin maleate, dibutyl tin diacetate, tinoctylate, dioctyl tin distearate, dioctyl tin dilaurate, dioctyl tindiethylmaleate, dioctyl tin diisooctylmaleate, dioctyl tin versatate andtin naphthenate;

tin alkoxides, e.g., dibutyl tin dimethoxide, dibutyl tin diphenoxideand dibutyl tin diisopropoxide;

tin oxides, e.g., dibutyl tin oxide and dioctyl tin oxide;

product of the reaction between dibutyl tin oxide and phthalate ester;

dibutyl tin bisacetylacetonate;

organoaluminum compounds, e.g., aluminum trisacetylacetonate, aluminumtrisethylacetoacetate and diisopropoxy aluminum ethylacetoacetate;

chelate compounds, e.g., zirconium tetraacetylacetonate and titaniumtetraacetylacetonate;

lead octylate;

amine-based compounds, and salts of these compounds and carboxylates,e.g., butylamine, octylamine, laurylamine, dibutylamine,monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine,triethylenetetramine, oleylamine, cyclohexylamine, benzylamine,diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine,diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine,N-methyl morpholine, 2-ethyl-4-methylimidazole and1,8-diazabicyclo(5,4,0) undecene-7 (DBU);

low-molecular-weight polyamide resins produced by the reactions betweenexcessive quantities of polyamines and polybasic acids;

products of the reactions between excessive quantities of polyamines andepoxy compounds;

amino-containing silane coupling agents, e.g., γ-aminopropyltrimethoxysilane and N-(β-aminoethyl)aminopropyl methyldimethoxysilane); and

other known silanol condensing catalysts, acidic or basic.

Of these catalysts, the more preferable ones are tetravalent tincompounds, in particular dialkoxy tin dialkoxides, more specificallydibutyl tin bisacetylacetonate, dibutyl tin dimethoxide and dibutyl tindipropoxide, when quick curing at room temperature is required. Theeffects of the present invention will be exhibited more significantlywhen the tetravalent tin compound, e.g., dialkyl tin dialkoxide, isused, because it shows essentially neither deactivation when mixed withwater or a hydrate of metallic salt in the curing agent, nordeterioration in curing speed after being stored.

These catalysts may be used either individually or in combination.

The silanol condensing catalyst (J) is incorporated in the curing agent(II) component preferably at about 0.1 to 20 parts by weight per 100parts by weight of the silyl-containing ethylene/α-olefin/non-conjugatedpolyene random copolymer rubber (A1) in the major ingredient (I), morepreferably 1 to 10 parts by weight. The silanol condensing catalyst (J)content below the above-mentioned range is undesirable, because ofinsufficient curing speed and insufficient extent of the curingreaction. The content beyond the above range is also undesirable,because it may cause local heating or foaming occurring during thecuring process to make it difficult to produce the cured product of goodproperties, and unacceptably short pot life. It is also undesirableviewed from its workability.

Water or Hydrate of a Metallic Salt (B11)

Of the water or hydrate of a metallic salt (B11) in the curing agent(II) component for the present invention, the hydrate of a metallic saltserves as the water source necessary for condensing/curing thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1) in the major ingredient (I) component, andpromotes formation of the crosslinked structures.

The common commercial hydrates of metallic salts can be widely used forthe present invention. They include hydrates of alkali-earth metals andother metals. The concrete examples of these hydrates include Al₂O₃.H₂O,Al₂O₃.3H₂O, Al₂(SO₄)₃.18H₂O, Al₂(C₂O₄)₃.4H₂O, AlNa(SO₄)₂.12H₂O,AlK(SO₄)₂.12H₂O, BaCl₂.2H₂O, Ba(OH)₂.8H₂O, CaSO₄.2H₂O, CaS₂O₃.6H₂O,Ca(NO₃)₂.4H₂O, CaHPO₄.2H₂O, Ca(C₂O₄).H₂O, Co(NO₃)₂.6H₂O,Co(CH₃COO)₂.4H₂O, CuCl₂.2H₂O, CuSO₄.5H₂O, FeCl₂.4H₂O, FeCl₃.6H₂O,FeSO₄.7H₂O, Fe(NH₄) (SO₄)₂.12H₂O, K₂CO₃.1.5H₂O, KNaCO₃.6H₂O, LiBr.2H₂O,Li₂SO₄.H₂O, MgSO₄.H₂O, MgSO₄.7H₂O, MgHPO₄.7H₂O, Mg₃(PO₄)₂.8H₂O,MgCO₃.3H₂O, Mg₄(CO₃)₃(OH)₂.3H₂O, MoO₃.2H₂O, NaBr.2H₂O, Na₂SO₃.7H₂O,Na₂SO₄.10H₂O, Na₂S₂O₃.5H₂O, Na₂S₂O₆.2H₂O, Na₂B₄O₇.10H₂O, NaHPHO₃.2.5H₂O,Na₃PO₄.12H₂O, Na₂CO₃.H₂O, Na₂CO₃.7H₂O, Na₂CO₃.10H₂O, NaCH₃COO.3H₂O,NaHC₂O₄.H₂O, NiSO₄.6H₂O, NiC₂O₄.2H₂O, SnO₂.nH₂O, NiC₂O₄.2H₂O,Sn(SO₄)₂.2H₂O, ZnSO₃.2H₂O, ZnSO₄.7H₂O, Zn₃(PO₄)₂.4H₂O andZn(CH₃COO)₂.2H₂O.

Of these, the hydrates of alkali and alkali-earth metals are morepreferable. The concrete examples of these hydrates include MgSO₄.7H₂O,Na₂CO₃.10H₂O, Na₂SO₄.10H₂O, Na₂S₂O₃.5H₂O, Na₃PO₄.12H₂O andNa₂B₄O₇.10H₂O.

These hydrates of metallic salts may be used either individually or incombination.

When water is used for the present invention, it is incorporatedpreferably at 0.01 to 25 parts by weight per 100 parts by weight of thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1), more preferably 0.05 to 15 parts, still morepreferably 0.2 to 5 parts by weight.

The hydrate of metallic salts is incorporated preferably at 0.01 to 50parts by weight per 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1),more preferably 0.1 to 30 parts, still more preferably 1 to 20 parts,most preferably 2 to 10 parts by weight.

The water and hydrates of metallic salts may be used either individuallyor in combination.

Other Components

The curable rubber composition (10) of the present invention may beincorporated with various additives.

These additives may be represented by tackifier, which is represented bysilane coupling agent, although not limited thereto.

The silane coupling agent is a compound having a group containingsilicon atom to which a hydrolyzable group is bonded (hereinafterreferred to as hydrolyzable silicon group) and one or more other groups.The examples of the hydrolyzable silicon group include those representedby the following general formula (1), preferably those represented bythe general formula (2):

wherein, R¹ and R² are each an alkyl group of 1 to 20 carbon atoms, arylgroup of 6 to 20 carbon atoms, aralkyl group of 7 to 20 carbon atoms, ortriorganosiloxy group represented by (R′)₃SiO— (R's are each ahydrocarbon group of 1 to 20 carbon atoms, which may be substituted ornot substituted;

X is a hydrolyzable group; and

“a” is an integer of 0 to 3, “b” is an integer of 0 to 2, wherein “a”and “b” are not simultaneously zero; and “m” is an integer of 0 to 19,

wherein, R², X and “a” are the same as those for the general formula(1).

These hydrolyzable groups include hydrogen atom, alkoxyl, acyloxy,ketoxymate, amino, amide, aminoxy, mercapto and alkenyloxy, which arecommonly used. Of these, the more preferable ones include methoxy andethoxy groups, because of their high hydrolysis speed. The silanecoupling agent preferably contains 2 or more hydrolyzable groups, morepreferably 3 or more.

The functional groups, other than the hydrolyzable silicon ones, usefulfor the present invention include primary, secondary and tertiary amino,mercapto, epoxy, carboxyl, vinyl, isocyanate and isocyanurate groups,and halogen atom.

Of these, the more preferable ones include primary, secondary andtertiary amino, epoxy, isocyanate and isocyanurate groups andparticularly preferable ones are isocyanate and epoxy groups.

The silane coupling agents useful for the present invention include:

amino-containing silanes, e.g., γ-aminopropyltrimethoxysilane,γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane,γ-(2-aminoethyl) aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyltriethoxysilane, γ-(2-aminoethyl) aminopropyltriethoxysilane,γ-ureidopropyltrimethoxysilane,n-β-(n-vinylbenzylaminoethyl)-γ-aminopropyltriethoxysilane andγ-anilinopropyltrimethoxysilane;

mercapto-containing silanes, e.g., γ-mercaptopropyltrimethoxysilane,γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilaneand γ-mercaptopropylmethyldiethoxysilane;

epoxy-containing silanes, e.g., γ-glycidoxypropyltrimethoxysilane,γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilaneand β-(3,4-epoxycyclohexyl)ethyltriethoxysilane;

carboxysilanes, e.g., β-carboxyethyltriethoxysilane,β-carboxyethylphenylbis(2-methoxyethoxy)silane andn-β-(carboxymethylaminoethyl)-γ-aminopropyltrimethoxysilane;

silanes containing a vinyl type unsaturated group, e.g.,vinyltrimethoxysilane, vinyltriethoxysilane,γ-methacryloyloxypropylmethyldimethoxysilane andγ-acryloyloxypropylmethyltriethoxysilane;

halogen-containing silanes, e.g., γ-chloropropyltrimethoxysilane;

silane isocyanurates, e.g., tris(trimethoxysilyl)isocyanurate; and

isocyanate-containing silanes, e.g., γ-isocyanate propyltrimethoxysilaneand γ-isocyanate propyltriethoxysilane.

Moreover, the modifications of these compounds as their derivatives arealso useful as the silane coupling agents. These compounds includeamino-modified silyl polymers, silylated amino polymers, unsaturatedaminosilane complexes, block isocyanate silanes, phenylamino-longchain-alkyl silanes aminosilylated silicone and silylated polyesters.

These silane coupling agents tend to be hydrolyzed easily in thepresence of moisture, but can be kept stable when incorporated in themajor ingredient (I) for the curable rubber composition (10) of thepresent invention.

It is needless to say that a compound having epoxy or isocyanate groupin the molecule (including isocyanate polymer) can be used as thetackifier other than a silane coupling agent without causing anyproblem.

These tackifiers may be used either individually or in combination.

The tackifier is incorporated for the present invention at 0.01 to 20parts by weight per 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1),particularly preferably 0.1 to 10 parts by weight.

The curable rubber composition (10) may be further modified with one ormore of various fillers.

The fillers useful for the present invention include:

reinforcing fillers, e.g., fumed silica, settling silica, silicicanhydride, silicic hydride, talc and carbon black;

other fillers, e.g., limestone powder, gelatinized calcium carbonate,diatomaceous earth, fired clay, clay, titanium oxide, bentonite, organicbentonite, ferric oxide, zinc oxide and activated zinc white; and

fibrous fillers, e.g., glass fibers or filaments.

Of these, the reinforcing silica, mainly of fumed silica, settlingsilica, silicic anhydride, silicic hydride, talc or carbon black, isused when the curable rubber composition of high strength is to beproduced. The cured product of high strength and modulus can beprepared, when it is incorporated at 1 to 100 parts by weight per 100parts by weight of the silyl-containing ethylene/α-olefin/non-conjugatedpolyene random copolymer rubber (A1) in the major ingredient (I) for thepresent invention.

On the other hand, when the cured product of low modulus and highelongation is to be produced, it is recommended to incorporate the othertype of filler, e.g., limestone powder, gelatinized calcium carbonate,diatomaceous earth, fired clay, clay, titanium oxide, bentonite, organicbentonite, ferric oxide, zinc oxide or activated zinc white at 5 to 400parts by weight per 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1) inthe major ingredient (I) for the present invention.

These fillers may be used either individually or in combination.

The filler may be incorporated in the major ingredient (I) component orcuring agent (II) component, or both.

When incorporated with a plasticizer in combination with the filler, thecurable rubber component (10) of the present invention will have one ormore additional advantages, e.g., further improved elongation of thecured product and a larger quantity of the filler being incorporated.

For the plasticizer, any commonly used one may be used. Preferably, itshould be compatible with the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1).

The concrete examples of the plasticizers include process oil,polybutene, hydrogenated polybutene, α-methyl styrene oligomer, liquidpolybutadiene, hydrogenated liquid polybutadiene, paraffin oil,naphthene oil and atactic polypropylene. Of these, more preferable onesare the hydrocarbon-based compounds free of unsaturated group, e.g.,process oil, hydrogenated polybutene, hydrogenated liquid polybutadiene,paraffin oil and naphthene oil.

The concrete examples of the plasticizers include process oil, paraffinoil, naphthene oil, polybutadiene and ethylene/α-olefin oligomer. Theplasticizer may be used in place of the solvent during the process ofintroducing a hydrolyzable silyl group into the above-describedethylene/α-olefin/non-conjugated polyene random copolymer rubber (A₀),for the purposes of, e.g., adjusting reaction temperature and viscosityof the reaction system.

The curable rubber composition (10) of the present invention may beadequately incorporated, as required, with various additives, e.g.,antioxidant, ultraviolet ray absorber, light stabilizer, flameretardant, thixotropy enhancer, pigment and surfactant, within limitsnot detrimental to the objects of the invention.

The curable rubber composition (10) of the present invention may be usedfor either two-liquid composition or liquid composition comprising threeor more types of liquids. When used for a two-liquid composition, forexample, the initial properties of the cured product can be stablyrealized, when the major ingredient (I) incorporated with filler,plasticizer or the like and the curable agent (II) incorporated withfiller, plasticizer or the like, separately prepared for the presentinvention, are mixed with each other immediately before the two-liquidcomposition is used, even after they are stored for extended periods.

The curable rubber composition (10) of the present invention is usefulmainly for a curable elastomer composition, which can be suitably usedas sealants for electric/electronic device members, civil engineeringworks (e.g., stopping water), buildings, ships automobiles and roads. Itis also useful for various types of adhesive compositions, because it isfast adhesive to widely varying base materials, e.g., glass, stone,ceramics, lumber, synthetic resins and metals, in the absence of primer.

The curable rubber composition (10) of the present invention isparticularly useful as a sealant for laminated glass, stably exhibitingits adhesion for extended periods for, e.g., float glass and varioustypes of surface-treated heat ray reflective glass, and spacers of purealuminum and aluminum produced by anodization.

Curable Rubber Composition (10) and its Uses

The curable rubber composition (10) of the present invention contains,as described earlier, the curable composition with the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber as thecomponent (A1). More concretely, the curable composition (10) of thepresent invention contains at least the major ingredient (I) containingthe organic polymer (Z), and a curing agent (II) containing a silanolcondensing catalyst (J) and water or a hydrate of a metallic salt (B11)It can be suitably used for electric/electronic device members,transportation machines, and civil engineering/construction, medical andleisure areas, as described earlier.

The curable rubber composition (10) of the present invention can be usedas sealants, potting agents, coating materials or adhesives forelectric/electronic device members, transportation machines, and civilengineering/construction, medical and leisure areas.

Rubber Composition (11)

The rubber composition (11) of the present invention contains thespecific silyl-containing ethylene/α-olefin/non-conjugated polyenerandom copolymer rubber (A2) and an organosilicon polymer (K1).

The silyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A2) (hereinafter sometimes referred to as“silyl-containing copolymer rubber (A2)) contains a hydrolyzable silylgroup, represented by the following general formula (1), preferablyhaving a structural unit derived from a norbornene compound as thenon-conjugated polyene with at least one specific terminal vinyl group,represented by the above-described general formula (4) or (5), and thehydrolyzable silyl group represented by the following general formula(1) in the side chain or at the terminal of theethylene/α-olefin/non-conjugated polyene random copolymer rubber:

wherein, R is a monovalent hydrocarbon group of 1 to 12 carbon atoms,which may be substituted or not substituted, preferably a monovalenthydrocarbon group not having aliphatic unsaturated bonds, e.g., alkylgroup (e.g., methyl, ethyl, propyl, butyl, hexyl or cyclohexyl), arylgroup (e.g., phenyl or tolyl) or the above-described group whosehydrogen atom bonded to the carbon atom is totally or partly substitutedwith a halogen (e.g., fluorine); X is a group selected from the groupconsisting of hydride, halogen, alkoxyl, acyloxy, ketoxymate, amide,acid amide, aminoxy, thioalkoxy, amino, mercapto and alkenyloxy, ofwhich alkoxyl, in particular having 1 to 4 carbon atoms, is morepreferable; and “m” is an integer of 0 to 2, preferably 0 or 1.

The silyl group represented by the general formula (1) is the same asthe hydrolyzable silyl group represented by the general formula [III]for the ethylene/α-olefin/non-conjugated polyene random copolymer rubber(A1).

The silyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A2) normally has at least one type of silyl grouprepresented by the following general formula (2) or (3):

wherein, R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; R¹is hydrogen atom or an alkyl group of 1 to 10 carbon atoms; R² ishydrogen atom or an alkyl group of 1 to 5 carbon atoms; R³ is hydrogenatom or an alkyl group of 1 to 10 carbon atoms; X is a hydrolyzablegroup selected from the group consisting of hydride, halogen, alkoxyl,acyloxy, ketoximate, amide, acid amide, aminoxy, thioalkoxy, amino,mercapto and alkenyloxy group; and “m” is an integer of 0 to 2 and “n”is an integer of 0 to 10.

R, X and “m” in the general formulae (2) and (3) are the same as thosein the general formula (1), and R¹, R², R³ and “n” are the same as thosein the general formulae [I] and [II].

The silyl-containing copolymer rubber (A2) has one or more silyl groupsin the molecule, preferably 0.1 to 10 groups on the average. It will nolonger exhibit good rubber elasticity, due to insufficient curability,when it contains less than 0.1 silyl groups.

The method of producing the ethylene/α-olefin/non-conjugated polyenerandom copolymer rubber containing a hydrolyzable silyl group is notlimited. However, it is particularly preferably produced by thehydrosilylation, wherein an ethylene/α-olefin/non-conjugated polyenerandom copolymer rubber having a norbornene compound as thenon-conjugated polyene with at least one terminal vinyl grouprepresented by the general formula (4) or (5) is reacted with a siliconcompound represented by the following general formula (6):

The ethylene/α-olefin/non-conjugated polyene random copolymer rubber(A2) to be reacted with the silicon compound represented by the generalformula (6) is a random copolymer of ethylene, an α-olefin of 3 to 20carbon atoms, and non-conjugated polyene.

The α-olefin of 3 to 20 carbon atoms is the same as one of the concreteexamples of the α-olefin of 3 to 20 carbon atoms which constitutes thethe silyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1). The α-olefin is preferably that of 3 to 10 carbonstoms, more preferably propylene, 1-butene, 1-hexene, 1-octene or thelike.

These α-olefins may be used either individually or in combination.

The non-conjugated polyene suitably used for the present invention is anorbornene compound with a terminal vinyl group represented by thegeneral formula (4) or (5):

The general formulae (4) and (5) are each the same as the respectivegeneral formulae [I] and [II]. Therefore, the concrete examples of thenorbornene compounds can be the same as those represented by the generalformulae [I] and [II]. Of these, the more preferable ones include5-vinyl-2-norbornene, 5-methylene-2-norbornene,5-(2-propyenyl)-2-norbornene, 5-(3-butenyl)-2-norbornene,5-(4-pentenyl)-2-norbornene, 5-(5-hexenyl)-2-norbornene,5-(6-heptenyl)-2-norbornene and 5-(7-octenyl)-2-norbornene.

These norbornene compounds may be used either individually or incombination.

A non-conjugated polyene may be used, in addition to the above-describedone, e.g., 5-vinyl-2-norbornene, within limits not detrimental to theobject of the present invention.

More concretely, these non-conjugated polyenes include:

linear non-conjugated polyenes, e.g., 1,4-hexadiene,3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene,4,5-dimethyl-1,4-hexadiene and 7-methyl-1,6-octadiene;

cyclic non-conjugated polyenes, e.g., methyltetrahydroindene,5-ethylidene-2-norbornene, 5-methylene-2-norbornene,5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene,6-chloromethyl-5-isopropenyl-2-norbornene and dicyclopentadiene; and

trienes, e.g., 2,3-diisopropylidene-5-norbornene,2-ethylidene-3-isopropylidene-5-norbornene and2-propenyl-2,2-norbornadiene.

The ethylene/α-olefin/non-conjugated polyene random copolymer rubbercomposed of the above components has the following properties.

(i) Molar Ratio of ethylene to α-olefin of 3 to 20 Carbon Atoms(ethylene/α-olefin)

The ethylene/α-olefin/non-conjugated polyene random copolymer rubbercontains the (a) unit derived from

ethylene and the (b) unit of α-olefin of 3 to 20 carbon atoms(hereinafter sometimes referred to as merely α-olefin) in a molar ratioof 40/60 to 95/5, preferably 50/50 to 90/10, more preferably 55/45 to85/15, still more preferably 60/40 to 80/20 [(a)/(b) molar ratio].

The random copolymer rubber can give, when it has an (a)/(b) molar ratioin the above range, a rubber composition which is formed into avulcanized rubber shape excellent in resistance to aging under heating,strength characteristics and rubber elasticity, and, at the same time,excellent in moldability and resistance to cold temperature.

(ii) Iodine Value

The ethylene/α-olefin/non-conjugated polyene random copolymer rubber hasan iodine value of 0.5 to 50 (g/100 g), preferably 0.8 to 40 (g/100 g),more preferably 1 to 30 (g/100 g), still more preferably 1.5 to 25(g/100 g), wherein the iodine value corresponds to quantity of thedouble bond contained in the structural unit derived from the norbornenecompound with a terminal vinyl group, represented by the general formula(4) or (5).

The random copolymer rubber can give, when it has an iodine value in theabove range, a desired content of the hydrolyzable silyl group, and arubber composition which is formed into a vulcanized rubber shapeexcellent in compression-resistant permanent set and resistant to agingunder service conditions (under heating). An iodine value exceeding 50is disadvantageous costwise and hence undesirable.

(iii) Intrinsic Viscosity

The ethylene/α-olefin/non-conjugated polyene random copolymer rubber hasan intrinsic viscosity [η] of 0.001 to 2 dl/g, determined in decalinkept at 135° C., preferably 0.01 to 2 dl/g, more preferably 0.05 to 1.0dl/g, still more preferably 0.05 to 0.7 dl/g, most preferably 0.1 to 0.5dl/g.

The random copolymer rubber can give, when it has an intrinsic viscosity[η] in the above range, a highly fluid rubber composition which isformed into a crosslinked rubber shape excellent in strength propertiesand compression-resistant permanent set.

(iv) Molecular Weight Distribution (Mw/Mn)

The ethylene/α-olefin/non-conjugated polyene random copolymer rubber hasa molecular weight distribution (Mw/Mn) of 3 to 100, determined by gelpermeation chromatography (GPC), preferably 3.3 to 75, more preferably3.5 to 50.

The random copolymer rubber can give, when it has a molecular weightdistribution (Mw/Mn) in the above range, a rubber composition which isformed into a crosslinked rubber shape excellent in fabricability andstrength properties.

The ethylene/α-olefin/non-conjugated polyene random copolymer rubber isproduced by random copolymerization with ethylene, an α-olefin of 3 to20 carbon atoms and norbornene compound with a vinyl group at theterminal, represented by the general formula (4) or (5), by the methodsimilar to that for the ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A₀). The copolymerization is preferably effected in ahydrocarbon solvent.

The method of producing the ethylene/α-olefin/non-conjugated polyenerandom copolymer rubber containing the modified silyl group byhydrosilylation, wherein the ethylene/α-olefin/non-conjugated polyenerandom copolymer rubber is reacted with a silicon compound representedby the general formula (6), is similar to that for the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1).

In the hydrosilylation reaction described above, the SiH group in thesilicon compound represented by the general formula (6) is added to thedouble bond derived from the non-conjugated polyene in theethylene/α-olefin/non-conjugated polyene random copolymer rubber, toform the silyl-containing structure represented by the general formula(2) or (3), when the non-conjugated polyene is represented by thegeneral formula (4) or (5), respectively.

It is possible to add a siloxane with hydrogen modified at one terminal,represented by the following general formula (7), in combination withthe silicon compound represented by the general formula (6), to impartthe resistance to weather, slippage and gas permeability as thecharacteristics of siloxane to the copolymer rubber:

wherein, R⁴ is a monovalent hydrocarbon group of 1 to 12 carbon atoms,which maybe substituted or not substituted, particularly preferably analkyl group; and “p” is an integer of 5 to 200, particularly preferably10 to 150.

The silyl-containing copolymer rubber (A2) is present in the rubbercomposition (11) of the present invention preferably at 10% or more,more preferably 20% or more, still more preferably 30% or more.

The rubber composition (11) of the present invention is incorporatedwith an organosilicon polymer (K1), to decrease its viscosity andthereby to make it more easily handled, increase curing speed, andattenuate tackiness of the cured product surface.

The organosilicon polymer (K1) for the present invention is a polymerhaving the siloxane bond as the main skeleton with the silicon atomhaving organic groups and oxygen atom appearing alternately. One of theexamples is a polymer represented by the general formula (8):

wherein, R⁴, R⁵, R⁶ and R⁷ are each a non-hydrolyzable organic group of1 to 12 carbon atoms or X (which is the same as that for the generalformula (1)), which may be the same or different, at least one of R⁴ toR⁶ is a non-hydrolyzable organic group, and R⁵ and R⁶ may be bonded toeach other to form a ring; and “q” is an integer of 1 to 5000,preferably 5 to 100.

The concrete examples of the non-hydrolyzable organic groups of 1 to 12carbon atoms include alkyl groups, e.g., methyl and ethyl; cycloalkylgroups, e.g., cyclohexyl; aryl groups, e.g., phenyl; and aralkyl groups,e.g., benzyl.

The concrete examples of X include those for the general formula (1).The q-R⁴'s for the general formula (5) are not necessarily the same, andso are q-R⁵'s.

There are widely varying organosilicon polymers useful for the presentinvention as those represented by K1, e.g., those disclosed by JapanesePatent Publication No. 38987/1984, Japanese Patent Laid-Open PublicationNos. 60558/1980, 78055/1980, 145147/1982, 190043/1982, 25837/1984 and23643/1986, and “9586 Chemical Commodities” (published by Kagaku KogyoNippoh on Jan. 30, 1986, pp. 721 to 727). More concretely, they includesilicone oil, e.g., dimethyl silicone oil and methylphenyl silicone oil;and organopolysiloxanes, e.g., those having the above-described organicgroup, e.g., alkyl, cycloalkyl, aryl or aralkyl. They may be used eitherdirectly or in the form of copolymer, e.g., block or graft copolymerwith an organic polymer, e.g., alkyd resin, epoxy resin, polyesterresin, urethane resin, acrylic resin, polyethylene oxide, polypropyleneoxide, ethylene oxide/propylene oxide copolymer, polybutylene oxide orpolytetrahydrofuran.

The organosilicon polymers (K1) for the present invention also includethe above-described copolymers, silicone oil and organopolysiloxane intowhich a reactive silicon group, e.g., that represented by the generalformula (1), is introduced, and the organopolysiloxane having ahydrolyzable group, e.g., hydrogen atom bonded to the silicon atom inmethyl hydrogen silicone oil, and hydroxyl group.

Of the above-described organosilicon polymers (K1), those in the form ofliquid or having fluidity are more suitable, because they can be handledmore easily.

Those organosilicon polymers (K1) having hydroxyl or hydrolyzable groupbonded to the silicon atom are suitable, because they can react with thesilyl-containing copolymer rubber (A2) during the curing process,bringing about various advantages, e.g., prevented bleeding of theorganosilicon polymers (K1), controlled decline of their modulus ofelasticity and elongation even after they are in service in many cycles,and prevented surface tackiness.

The copolymer of the organopolysiloxane and organic polymer may besynthesized by the method disclosed by Japanese Patent Laid-OpenPublication No. 145147/1982, although not limited thereto.

Of the organosilicon polymers (K1), polysiloxanes having 2 or moresilanol groups are particularly suitable. These polysiloxanes can give arubber composition, excellent particularly in curability deep inside(measure of curing speed inside of a thick cured product), and capableof imparting excellent resistance to weather and heat, among others, tothe cured product.

Widely varying common polysiloxanes now commercially available can beused for the present invention. In particular, those compatible with the(A2) component can give the cured product of higher stability. It istherefore preferable to use a polysiloxane of relatively low molecularweight, e.g., that having 50 or less silicon atoms in the molecule. Someof the concrete examples of these polysiloxane structures are describedbelow:

wherein, Me is methyl group and Ph is phenyl group, which hold inEXAMPLES described below).

These organosilicon polymers (K1) may be used either individually or incombination.

Content of the organosilicon polymers (K1) cannot be sweepinglygeneralized, because it depends on, e.g., desired Mooney viscosity(ML(1+4) at 100° C.), the obtained rubber composition and type of theorganosilicon polymer (K1) used. It is however recommended that theorganosilicon polymer (K1) is incorporated normally at around 1 to 1000parts by weight per 100 parts by weight of the (A2) component,preferably around 10 to 150 parts.

When a polysiloxane having 2 or more silanol groups as the organosiliconpolymer (K1), it is recommended that the organosiliconpolymer (K1) isincorporated in such a way to have around 0.1 to 8, preferably around0.3 to 4, hydroxyl groups bonded to the silicon atom in the polysiloxaneper one hydrolyzable group in the (A2) component.

In the present invention, it is preferable to incorporate thepolysiloxane at around 20 to 120 parts by weight per 100 parts by weightof the (A2) component, more preferably around 25 to 100 parts. Anexcessively low content of the polysiloxane is undesirable, because itmay result in the resin composition of insufficient curability deepinside. On the other hand, an excessively high content of thepolysiloxane is also undesirable, because it may deteriorate thetensile-related characteristics of the cured product.

The cured product of the rubber composition (11) of the presentinvention has good resistance to, e.g., weather, heat and water, andretains the excellent characteristics of high strength and elongation,which come from the cured product of the (A2) component, and alsoexhibit good effects coming from the (K1) component, e.g., reducedviscosity to improve workability and prevented surface tackiness.

In the present invention, the organosilicon polymer (K1) may be used inplace of the solvent during the process of introducing a reactivesilicon group into the above-described ethylene/α-olefin/non-conjugatedpolyene random copolymer rubber, for the purposes of, e.g., adjustingreaction temperature and viscosity of the reaction system.

The rubber composition (11) of the present invention is preferablyincorporated with a curing catalyst which promotes the silanolcondensation.

Widely varying known curing catalysts may be used for the presentinvention. The concrete examples of these catalysts useful for thepresent invention include titanate esters, e.g., those of tetrabutyltitanate and tetrapropyl titanate; tin carboxylates, e.g., dibutyl tindilaurate, dibutyl tin maleate, dibutyl tin diacetate, tin octylate andtin naphthenate; product of the reaction between dibutyl tin oxide andphthalate ester; dibutyl tin acetylacetonate; organoaluminum compounds,e.g., aluminum trisacetylacetonate, aluminum trisethylacetoacetate anddiisopropoxy aluminum ethylacetoacetate; chelate compounds, e.g.,zirconium tetraacetylacetonate and titanium tetraacetylacetonate; leadoctylate; amine-based compounds, and salts of these compounds andcarboxylates, e.g., butylamine, octylamine, dibutylamine,monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine,triethylenetetramine, oleylamine, cyclohexylamine, benzylamine,diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine,diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine,N-methyl morpholine, 2-ethyl-4-methylimidazole and1,8-diazabicyclo(5,4,0) undecene-7 (DBU); low-molecular-weight polyamideresins produced by the reactions between excessive quantities ofpolyamines and polybasic acids; products of the reactions betweenexcessive quantities of polyamines and epoxy compounds; and knownsilanol condensing catalysts, e.g., silane coupling agents containingamino group (e.g., γ-aminopropyl trimethoxy silane andN-(β-aminoethyl)aminopropylmethyldimethoxy silane), and other knowncatalysts, acidic or basic. These compounds may be used eitherindividually or in combination.

The curing catalyst, when used, is incorporated normally at 0.1 to 20parts by weight per 100 parts by weight of the (A2) component,preferably around 1 to 10 parts by weight. An excessively low content ofthe catalyst is undesirable, because it may result in slow curing speedof the resin composition product. On the other hand, an excessively highcontent of the catalyst is also undesirable, because it may deterioratethe tensile-related characteristics of the cured product.

The rubber composition (11) of the present invention may be adequatelyincorporated with one or more additives. The additives useful for thepresent invention include adhesion improver, property adjuster, storagestability improver, plasticizer, filler; aging inhibitor, ultravioletray absorber, metal deactivator, ozone-caused aging inhibitor, lightstabilizer, amine-based radical chaining inhibitor, phosphorus-basedperoxide decomposer, lubricant, pigment, and foaming agent.

The adhesion improvers useful for the present invention include commonlyused adhesives and silane coupling agents, e.g., aminosilane andepoxysilane compounds; and others.

The concrete examples of these adhesion improvers include phenolicresins, epoxy resins, γ-aminopropyl trimethoxysilane,N-(β-aminoethyl)aminopropyl methyldimethoxysilane, coumarone/indeneresins, rosin ester resins, terpene/phenol resins, α-methylstyrene/vinyl toluene copolymers, polyethylmethyl styrene, alkyltitanates, and aromatic polyisocyanate. The adhesion improver, whenused, is incorporated preferably at about 1 to 50 parts by weight per100 parts by weight of the totaled (A2) and (K1) components, morepreferably about 5 to 30 parts by weight.

The storage stability improvers useful for the present invention includecompounds with silicon to which a hydrolyzable group is bonded, andesters of ortho-organic acids (other than an alkyl orthoformate).

The concrete examples of the storage stability improvers includemethyltrimethoxy silane, methyltriethoxy silane, tetramethoxy silane,ethyltrimethoxy silane, dimethyldiethoxy silane,trimethylisobutoxysilane, trimethyl (n-butoxy) silane, n-butyltrimethoxysilane, and methyl orthoformate. The storage stability improver, whenused, is incorporated preferably at about 0.5 to 20 parts by weight per100 parts by weight of the totaled (A2) and (K1) components, morepreferably about 1 to 10 parts.

The plasticizer useful for the present invention is also not limited,and any commonly used one may be used. Preferably, it should becompatible with each component for the rubber composition (11) of thepresent invention.

The concrete examples of these plasticizers include hydrocarbon-basedcompounds, e.g., polybutene, hydrogenated polybutene, ethylene/α-olefinoligomer, α-methyl styrene oligomer, biphenyl, triphenyl, triaryldimethane, alkylene triphenyl, liquid polybutadiene, hydrogenated liquidpolybutadiene, alkyl diphenyl, partially hydrogenated ter-phenyl,paraffin oil, naphthene oil and atactic polypropylene; parafinchlorides; phthalate esters, e.g., those of dibutyl phthalate, diheptylphthalate, di(2-ethylhexyl) phthalate, butyl benzyl phthalate and butylphthalyl butyl glycolate; non-aromatic, dibasic acid esters, e.g., thoseof dioctyl adipate and dioctyl cebacate; esters of polyalkylene glycol,e.g., those of diethylene glycol benzoate and triethylene glycoldibenzoate; and phosphate esters, e.g., those of tricresyl phosphate andtributyl phosphate. They may be used either individually or incombination.

Of these, hydrocarbon-based compounds free of unsaturated group, e.g.,hydrogenated polybutene, hydrogenated liquid polybutadiene, paraffinoil, naphthene oil and atactic polypropylene, are more preferable forvarious reasons, e.g., high compatibility with each component for therubber composition (11) of the present invention, limited effects oncuring speed of the rubber composition, good resistance to weather ofthe cured product, and cheapness.

The plasticizer may be used in place of the solvent during the processof introducing a reactive silicon group into theethylene/α-olefin/non-conjugated polyene random copolymer rubber, forthe purposes of, e.g., adjusting reaction temperature and viscosity ofthe reaction system.

The plasticizer is incorporated preferably at about 10 to 500 parts byweight per 100 parts by weight of the totaled (A2) and (K1) components,more preferably about 20 to 300 parts by weight.

The concrete examples of the fillers include wood powder, pulp, cottonchips, asbestos, glass fibers, carbon fibers, mica, walnut shell powder,rice hull powder, graphite, diatomaceous earth, white clay, fumedsilica, settling silica, silicic anhydride, carbon black, calciumcarbonate, clay, talc, titanium oxide, magnesium carbonate, quartz, finealuminum powder, flint powder, and zinc powder. Of these, morepreferable ones are thixotropic fillers, e.g., settling silica, fumedsilica and carbon black; and calcium carbonate, titanium oxide and talc.The filler, when used, is incorporated preferably at about 10 to 500parts by weight per 100 parts by weight of the totaled (A2) and (K1)components, more preferably about 20 to 300 parts by weight.

The aging inhibitors useful for the present invention include commonlyused known ones, e.g., sulfur-based ones, radical inhibitors andultraviolet ray absorbers.

The sulfur-based aging inhibitors useful for the present inventioninclude mercaptans, salts thereof, sulfides including sulfidecarboxylate esters and hindered phenol-based sulfides, polysulfides,dithiocarboxylates, thioureas, thiophosphates, sulfonium compounds,thioaldehydes, thioketones, mercaptals, mercaptols, monothio acids,polythio acids, thioamides, and sulfoxides.

More concretely, the sulfur-based aging inhibitors include mercaptans,e.g., 2-mercaptobenzothiazole; salts of mercaptans, e.g., zinc salt of2-mercaptobenzothiazole; sulfides, e.g.,4,4′-thio-bis(3-methyl-6-t-butyl phenol),4,4′-thio-bis(2-methyl-6-t-butyl phenol),2,2′-thio-bis(4-methyl-6-t-butyl phenol),bis(3-methyl-4-hydroxy-5-t-butylbenzyl) sulfide, terephthaloyldi(2,6-dimethyl-4-t-butyl-3-hydroxybenzyl) sulfide, phenothiazine,2,2′-thio-bis (4-octyl phenol) nickel, dilauryl thiodipropionate,distearyl thiodipropionate, dimyristyl thiodipropionate, ditridecylthiodipropionate, distearylβ,β′-thiodibutyrate, lauryl-stearylthiodipropionate and 2,2-thio[diethyl-bis-3(3,5-di-t-butyl-4-hydroxyphenol)propionate]; polysulfides, e.g., 2-benzothiazole disulfide;dithiocarboxylates, e.g., zinc dibutyldithiocarbamate, zincdiethyldithiocarbamate, nickel dibutyldithiocarbamate, zincdi-n-butyldithiocarbamate, dibutyl ammonium dibutyldithiocarbamate, zincethyl-phenyl-dithiocarbamate and zinc dimethyldithiocarbamate;thioureas, e.g., 1-butyl-3-oxy-diethylene-2-thiourea,di-o-tolyl-thiourea and ethylene thiourea; and thiophosphates, e.g.,trilauryltrithiophosphate.

The above-described sulfur-based aging inhibitor preventsdecomposition/aging of the main chain under heating much moreefficiently than the other types for the curable rubber composition ofthe present invention, controlling the problems, e.g., residual surfacetackiness.

The radical inhibitors useful for the present invention includephenol-based ones, e.g., 2,2-methylene-bis(4-methyl-6-t-butyl phenol)and tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane; and amine-based ones, e.g., phenyl-β-naphthylamine,α-naphthylamine, N,N′-sec-butyl-p-phenylenediamine, phenothiazine andN,N′-diphenyl-p-phenylenediamine.

The ultraviolet ray absorbers useful for the present invention include2-(2′-hydroxy-3′,5′-di-t-butylphenyl) benzotriazole andbis(2,2,6,6-tetramethyl-4-piperidine) cebacate.

The aging inhibitor, when used, is incorporated at about 0.1 to 20 partsby weight per 100 parts by weight of the totaled (A2) and (K1)components, more preferably about 1 to 10 parts by weight.

The rubber composition (11) of the present invention contains the rubbercomposition with the ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber containing a hydrolyzable silyl group as the component(A2), wherein the organic polymer (Z1) containing a hydrolyzable silylgroup represented by the above-described general formula (1) andessentially no unsaturated double bond in the main chain can be preparedby uniformly kneading the components by a kneader, e.g., intermix mixer,planetary mixer, Banbury mixer, kneader or 2-roll unit.

The rubber composition (11) of the present invention is cured at roomtemperature to 200° C. for several minutes to several days, because itcan be cured quickly. It is particularly preferable to crosslink thecomposition with moisture in air at room temperature.

Curable Rubber Composition (11) and its Uses

The rubber composition (11) of the present invention contains the rubbercomposition with the ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber containing a hydrolyzable silyl group as the component(A2). More concretely, the crosslinkable rubber composition (11) of thepresent invention contains the organic polymer (Z1) and organosiliconpolymer (K1), the former containing a hydrolyzable silyl grouprepresented by the above-described general formula (1) and essentiallyno unsaturated double bond in the main chain. It can be suitably usedfor electric/electronic device members, transportation machines, andcivil engineering/construction, medical and leisure areas, as describedearlier.

The curable rubber composition (11) of the present invention can be usedas sealants, potting agents, coating materials or adhesives forelectric/electronic device members, transportation machines, and civilengineering/construction, and leisure areas.

Rubber Composition (12)

The rubber composition (12) of the present invention contains thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A2), an organic rubber (K2) and a crosslinking agent(M) for the organic rubber (K2).

The rubber composition (12) of the present invention contains thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A2) preferably at 10% or more, more preferably at 20%or more, still more preferably at 30% or more.

The organic rubbers (K2) for the rubber composition (12) of the presentinvention include polypropylene glycol-based rubber containing ahydrolyzable silyl group, polyisobutylene-based rubber containing ahydrolyzable silyl group, natural rubber, polyisoprene, polybutadiene,styrene/butadiene copolymer rubber, polychloroprene, acrylic rubber,acrylonitrile/butadiene copolymer rubber, ethylene/propylene copolymerrubber (EPM), ethylene/propylene/non-conjugated polyene copolymer rubber(EPDM), butyl rubber, urethane rubber, silicone rubber, epichlorohydrinrubber, ethylene/vinyl acetate copolymer rubber, ethylene/acryliccopolymer rubber, fluorine rubber, chlorosulfonated polyethylene, and acombination thereof.

Of these, polypropylene glycol-based rubber containing a hydrolyzablesilyl group, polyisobutylene-based rubber containing a hydrolyzablesilyl group, natural rubber, polyisoprene, polybutadiene,styrene/butadiene copolymer rubber, polychloroprene, acrylic rubber,acrylonitrile/butadiene copolymer rubber, ethylene/propylene copolymerrubber (EPM), ethylene/propylene/non-conjugated polyene copolymer rubber(EPDM), butyl rubber, urethane rubber, ethylene/acrylic copolymerrubber, silicone rubber and a combination thereof are particularlypreferable, for their compatibility with the (A2) component.

The other rubbers may be suitably used in the presence of a solubilizer.

The ratio of the silyl-containing ethylene/α-olefin/non-conjugatedpolyene random copolymer rubber (A2) to organic rubber (K2), i.e.,(A2)/(K2) ratio, is normally 3/97 to 70/30 by weight, preferably 5/95 to50/50 by weight, viewed from balances among formability of thethree-dimensional crosslinked structures, moldability and mechanicalstrength.

The crosslinking agent (M) useful for the organic rubber (K2) of thepresent invention is not limited, so long as it is normally used as avulcanization agent for rubber and serviceable for EPDM. For example,the crosslinking agents useful for the present invention include sulfur,sulfur donor, low-sulfur high-efficiency vulcanization promoter,quinoide, resin, peroxide and compound containing SiH group.

Others useful as the crosslinking agents (M) for the present inventioninclude multi-functional ones, having two or more functional groupsreactive with the crosslinking group in the organic rubber (K2). Thesefunctional groups include amino, isocyanate, maleimide, epoxy,hydrosilyl and carboxyl.

The rubber composition (12) of the present invention may be incorporatedwith a curing catalyst which promotes the silanol condensation. Widelyvarying known curing catalysts maybe used for the present invention. Theconcrete examples of these catalysts useful for the present inventioninclude titanate esters, e.g., those of tetrabutyl titanate andtetrapropyl titanate; tin carboxylates, e.g., dibutyl tin dilaurate,dibutyl tin maleate, dibutyl tin diacetate, tin octylate and tinnaphthenate; product of the reaction between dibutyl tin oxide andphthalate ester; dibutyl tin diacetylacetonate; organoaluminumcompounds, e.g., aluminum trisacetylacetonate, aluminumtrisethylacetoacetate and diisopropoxy aluminum ethylacetoacetate;chelate compounds, e.g., zirconium tetraacetylacetonate and titaniumtetraacetylacetonate; lead octylate; amine-based compounds, and salts ofthese compounds and carboxylates, e.g., butylamine, octylamine,dibutylamine, monoethanolamine, diethanolamine, triethanolamine,diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine,benzylamine, diethylaminopropylamine, xylylenediamine,triethylenediamine, guanidine, diphenylguanidine,2,4,6-tris(dimethylaminomethyl) phenol, morpholine, N-methylmorpholine,2-ethyl-4-methylimidazole and 1,8-diazabicyclo(5,4,0) undecene-7 (DBU);low-molecular-weight polyamide resins produced by the reactions betweenexcessive quantities of polyamines and polybasic acids; products of thereactions between excessive quantities of polyamines and epoxycompounds; and known silanol condensing catalysts, e.g., silane couplingagents containing amino group (e.g., γ-aminopropyl trimethoxy silane andN-(β-aminoethyl)aminopropylmethyldimethoxy silane) and other knowncatalysts, acidic or basic. These compounds may be used eitherindividually or in combination.

The curing catalyst, when used, is incorporated normally at 0.1 to 20parts by weight per 100 parts by weight of the (A2) component,preferably around 1 to 10 parts by weight. An excessively low content ofthe catalyst is undesirable, because it may result in slow curing speedof the rubber composition product. On the other hand, an excessivelyhigh content of the catalyst is also undesirable, because it maydeteriorate the tensile-related characteristics of the cured product.

The rubber composition (12) of the present invention may be adequatelyincorporated with one or more additives. The additives useful for thepresent invention include adhesion improver, property adjuster, storagestability improver, plasticizer, filler, aging inhibitor, ultravioletray absorber, metal deactivator, ozone-caused aging inhibitor, lightstabilizer, amine-based radical chaining inhibitor, phosphorus-basedperoxide decomposer, lubricant, pigment, and foaming agent.

The adhesion improvers useful for the present invention include commonlyused adhesives and others, except a silane coupling agent as the silanolcondensing catalyst. The concrete examples of these adhesion improversinclude phenolic resin, epoxy resin, coumarone/indene resin, rosin esterresin, terpene/phenol resin, α-methyl styrene/vinyl toluene copolymer,polyethylmethyl styrene, alkyl titanate, and aromatic polyisocyanate.The adhesion improver, when used, is incorporated preferably at about 1to 50 parts by weight per 100 parts by weight of the (A2) component,more preferably about 5 to 30 parts.

The storage stability improvers useful for the present invention includecompounds with silicon to which a hydrolyzable group is bonded, andesters of ortho-organic acids. The concrete examples of the storagestability improvers include methyltrimethoxy silane, methyltriethoxysilane, tetramethoxy silane, ethyltrimethoxy silane, dimethyldiethoxysilane, trimethylisobutoxy silane, trimethyl(n-butoxy) silane,n-butyltrimethoxy silane, and methyl orthoformate. The storage stabilityimprover, when used, is incorporated preferably at about 0.5 to 20 partsby weight per 100 parts by weight of the (A2) component, more preferablyabout 1 to 10 parts by weight.

The plasticizer useful for the present invention is also not limited,and any commonly used one may be used. Preferably, it should becompatible with each component for the rubber composition (12) of thepresent invention.

The concrete examples of these plasticizers include hydrocarbon-basedcompounds, e.g., polybutene, hydrogenated polybutene, ethylene/α-olefinoligomer, α-methyl styrene oligomer, biphenyl, triphenyl, triaryldimethane, alkylene triphenyl, liquid polybutadiene, hydrogenated liquidpolybutadiene, alkyl diphenyl, partially hydrogenated ter-phenyl,paraffin oil, naphthene oil and atactic polypropylene; parafinchlorides; phthalate esters, e.g., those of dibutyl phthalate, diheptylphthalate, di(2-ethylhexyl) phthalate, butyl benzyl phthalate and butylphthalyl butyl glycolate; non-aromatic, dibasic acid esters, e.g., thoseof dioctyl adipate and dioctyl cebacate; esters of polyalkylene glycol,e.g., those of diethylene glycol benzoate and triethylene glycoldibenzoate; and phosphate esters, e.g., those of tricresyl phosphate andtributyl phosphate. They may be used either individually or incombination.

Of these, hydrocarbon-based compounds free of unsaturated group, e.g.,hydrogenated polybutene, hydrogenated liquid polybutadiene, paraffinoil, naphthene oil and atactic polypropylene, are more preferable forvarious reasons, e.g., high compatibility with each component for therubber composition (12) of the present invention, limited effects oncuring speed of the rubber composition, good resistance to weather ofthe cured product, and cheapness.

The plasticizer may be used in place of the solvent during the processof introducing a reactive silicon group into theethylene/α-olefin/non-conjugated polyene random copolymer rubber, forthe purposes of, e.g., adjusting reaction temperature and viscosity ofthe reaction system.

The plasticizer, when used, is incorporated preferably at about 10 to500 parts by weight per 100 parts by weight of the (A2) component, morepreferably about 20 to 300 parts by weight.

The concrete examples of the fillers include wood powder, pulp, cottonchips, asbestos, glass fibers, carbon fibers, mica, walnut shell powder,rice hull powder, graphite, diatomaceous earth, white clay, fumedsilica, settling silica, silicic anhydride, carbon black, calciumcarbonate, clay, talc, titanium oxide, magnesium carbonate, quartz, finealuminum powder, flint powder, and zinc powder. Of these, morepreferable ones are thixotropic fillers, e.g., settling silica, fumedsilica and carbon black; and calcium carbonate, titanium oxide and talc.The filler, when used, is incorporated preferably at about 10 to 500parts by weight per 100 parts by weight of the (A2) component, morepreferably about 20 to 300 parts by weight.

The aging inhibitors useful for the present invention include commonlyused known ones, e.g., sulfur-based ones, radical inhibitors andultraviolet ray absorbers.

The sulfur-based aging inhibitors useful for the present inventioninclude mercaptans, salts thereof, sulfides including sulfidecarboxylate esters and hindered phenol-based sulfides, polysulfides,dithiocarboxylates, thioureas, thiophosphates, sulfonium compounds,thioaldehydes, thioketones, mercaptals, mercaptols, monothio acids,polythio acids, thioamides, and sulfoxides. The concrete examples of thesulfur-based aging inhibitors include mercaptans, e.g.,2-mercaptobenzothiazole; salts of mercaptans, e.g., zinc salt of2-mercaptobenzothiazole; sulfides, e.g.,4,4′-thio-bis(3-methyl-6-t-butyl phenol),4,4′-thio-bis(2-methyl-6-t-butyl phenol),2,2′-thio-bis(4-methyl-6-t-butyl phenol),bis(3-methyl-4-hydroxy-5-t-butylbenzyl) sulfide, terephthaloyldi(2,6-dimethyl-4-t-butyl-3-hydroxybenzyl) sulfide, phenothiazine,2,2′-thio-bis(4-octyl phenol) nickel, dilauryl thiodipropionate,distearyl thiodipropionate, dimyristyl thiodipropionate, ditridecylthiodipropionate, distearylβ,β′-thiodibutyrate, lauryl-stearylthiodipropionate and 2,2-thio[diethyl-bis-3(3,5-di-t-butyl-4-hydroxyphenol)propionate]; polysulfides, e.g., 2-benzothiazole disulfide;dithiocarboxylates, e.g., zinc dibutyldithiocarbamate, zincdiethyldithiocarbamate, nickel dibutyldithiocarbamate, zincdi-n-butyldithiocarbamate, dibutyl ammonium dibutyldithiocarbamate, zincethyl-phenyl-dithiocarbamate and zinc dimethyldithiocarbamate;thioureas, e.g., 1-butyl-3-oxy-diethylene-2-thiourea,di-o-tolyl-thiourea and ethylene thiourea; and thiophosphates, e.g.,trilauryltrithiophosphate.

The above-described sulfur-based aging inhibitor preventsdecomposition/aging of the main chain under heating much moreefficiently than the other types for the rubber composition of thepresent invention, controlling the problems, e.g., residual surfacetackiness.

The radical inhibitors useful for the present invention includephenol-based ones, e.g., 2,2-methylene-bis(4-methyl-6-t-butyl phenol)and tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane; and amine-based ones, e.g., phenyl-β-naphthylamine,α-naphthylamine, N,N′-sec-butyl-p-phenylenediamine, phenothiazine andN,N′-diphenyl-p-phenylenediamine.

The ultraviolet ray absorbers useful for the present invention include2-(2′-hydroxy-3′,5′-di-t-butylphenyl) benzotriazole andbis(2,2,6,6-tetramethyl-4-piperidine) cebacate.

The aging inhibitor, when used, is incorporated at about 0.1 to 20 partsby weight per 100 parts by weight of the (A2) component, more preferablyabout 1 to 10 parts by weight.

The rubber composition (12) of the present invention can be prepared byuniformly kneading the components by a kneader, e.g., intermix mixer,planetary mixer, Banbury mixer, kneader or 2-roll unit.

The rubber composition (12) of the present invention is cured at roomtemperature to 200° C. for several minutes to several days, because itcan be cured quickly. It is particularly preferable to crosslink thecomposition with moisture in air at room temperature.

Rubber Composition (12) and its Uses

The rubber composition (12) of the present invention contains thecurable composition with the ethylene/α-olefin/non-conjugated polyenerandom copolymer rubber containing a hydrolyzable silyl group as thecomponent (A2). More concretely, the rubber composition (12) of thepresent invention contains the organic polymer (Z1), organic rubber (K2)and a crosslinking agent (M) for the organic rubber (K2). It can besuitably used for electric/electronic device members, transportationmachines, and civil engineering/construction, medical and leisure areas,as described earlier.

The curable rubber composition (12) of the present invention can be usedas sealants, potting agents, coating materials or adhesives forelectric/electronic device members, transportation machines, and civilengineering/construction, and leisure areas.

Rubber Composition (13)

The rubber composition (13) of the present invention contains thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A2), an epoxy resin (K3), a silane coupling agent (N),a silanol condensing catalyst (O) and a curing agent for the epoxy resin(P).

The rubber composition (13) of the present invention contains thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A2) preferably at 10% or more, more preferably at 20%or more, still more preferably at 30% or more.

The epoxy resins (K3) for the rubber composition (13) of the presentinvention include epichlorohydrin-bisphenol A type epoxy resins;epichlorohydrin-bisphenol F type epoxy resins; epichlorohydrin-bisphenolS type epoxy resins; flame-retardant type epoxy resins (e.g., glycidylethers of tetrabromophenol A type); novolac type epoxy resins;hydrogenated bisphenol A type epoxy resins; glycidyl ether type epoxyresins of bisphenol A type propylene oxide adduct; glycidyl ether typeepoxy resins of bisphenol A type ethylene oxide adduct; glycidyl estertype epoxy resins, e.g., diglycidyl-p-oxybenzoate, phthalate diglycidylester, tetrahydrophthalate diglycidyl ester, hexahydrophthalatediglycidyl ester, and adipate diglycidyl ester; glycidyl amine typeepoxy resins, triglycidyl-m-aminophenol,N,N,N′,N′-tetraglycidylaminophenylmethane, N,N-diglycidylaniline, andN,N-diglycidyl-o-toluidine; hydantoin type epoxy resin, e.g.,1,3-diglycidyl-5-methyl-5-ethylhydantoin; triglycidyl isocyanurate;polyalkylene glycol diglycidyl ether; polyhydric alcohols (e.g.,glycerin and sorbitol) and glycidyl ether; alicyclic epoxy resins, e.g.,alicyclic diepoxy acetal, alicyclic diepoxy adipate, alicyclicdiepoxydiepoxy adipate, alicyclic diepoxy carboxylate, andvinylcyclohexene oxide; and epoxidized unsaturated polymers, e.g.,polybutadiene and oil-derived resins. The epoxy resins (K3) useful forthe present invention are not limited to the above, and commonly usedepoxy resins may be used. Of these epoxy resins, the more preferableones include those having two or more epoxy groups, because they producethe network structures more easily. Still more preferable ones includeepoxy resins having glycidyl ether, in particularepichlorohydrin-bisphenol A type epoxy resin, because of itscompatibility with the (A2) component.

The (K3) component, when used, is incorporated preferably 5 to 900 partsby weight per 100 parts by weight of the (A2) component, more preferably10 to 300 parts by weight. At below 5 parts, toughness of the epoxyresin will not be realized and insufficient cohesive force will result.At above 900 parts, on the other hand, the polymer as the (A2) componenthaving a reactive silicon group may not be included in the matrix of thecured product, with the result the cured product has insufficientelasticity and becomes fragile. Therefore, the content beyond the aboverange is undesirable.

The silane coupling agent (N) useful for the present invention isgenerally a silane containing a hydrolyzable silicon group and one ormore other functional groups in the molecule, and the functional groupsuseful for the present invention include primary, secondary and tertiaryamino, mercapto, epoxy, ureide, isocyanate, vinyl, methacryl andhalogenoalkyl. Of these, the more preferable ones include those having aprimary, secondary or tertiary amino, mercapto, epoxy or ureide group,which are reactive with both the polymer having a reactive silicon groupof (A2) component and the epoxy resin of (K3) component. Still morepreferable ones are those having an amide group, especially primary orsecondary. The hydrolyzable silicon groups useful for the presentinvention include those represented by the above-described generalformula (I) in which X is a hydrolyzable group. Alkoxyl is morepreferable, because of its easiness of handling, among others. Thesilane coupling agents useful for the present invention includeamino-containing silanes, e.g., γ-aminopropyltrimethoxysilane,γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane,γ-aminopropylmethyldiethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropyltriethoxysilane, γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropylmethyldiethoxysilane, γ-(5-aminopentyl)aminopropyltrimethoxysilane, γ-(5-aminopentyl)aminopropyltriethoxysilane, γ-(5-aminopentyl)aminopropyldimethoxysilane, γ-(5-aminopentyl)aminopropylmethyldiethoxysilane,N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane andγ-anilinopropyltrimethoxysilane; mercapto-containing silanes, e.g.,γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane,γ-mercaptopropylmethyldimethoxysilane andγ-mercaptopropylmethyldiethoxysilane; epoxy-containing silanes, e.g.,γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane,γ-glycidoxypropylmethyldimethoxysilane,γ-glycidoxypropylmethyldiethoxysilane,β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane;β-(3,4-epoxycyclohexyl)ethyltriethoxysilane;β-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane;β-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane; and ureido-containingsilanes, e.g., γ-ureidopropyltrimethoxysilane,γ-ureidopropyltriethoxysilane, γ-ureidopropylmethyldimethoxysilane andγ-ureidopropylmethyldiethoxysilane. These silane coupling agents (N) maybe used either individually or in combination.

The (N) component is incorporated preferably at 0.01 to 50 parts byweight per 100 parts by weight of the (A2) component. At the (N) contentbeyond the above range, the layered structure cannot be effectivelycontrolled, and, in particular, insufficient interfacial adhesion willresult at below 0.01 part by weight, and hence undesirable. It isincorporated more preferably at 0.1 to 5 parts by weight.

The silanol condensing catalysts (O) useful for the present inventioninclude titanate esters, e.g., those of tetrabutyl titanate andtetrapropyl titanate; organotin compounds, e.g., dibutyl tin dilaurate,dibutyl tin maleate, dibutyl tin diacetate, tin octylate, tinnaphthenate, product of the reaction between dibutyl tin oxide andphthalate ester and dibutyl tin diacetylacetonate; organoaluminumcompounds, e.g., aluminum trisacetylacetonate, aluminumtrisethylacetoacetate and diisopropoxy aluminum ethylacetoacetate;chelate compounds, e.g., zirconium tetraacetylacetonate and titaniumtetraacetylacetonate; organolead compounds, e.g., lead octylate;amine-based compounds, and salts of these compounds and carboxylates,e.g., butylamine, octylamine, laurylamine, dibutylamine,monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine,triethylenetetramine, oleylamine, cyclohexylamine, benzylamine,diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine,diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine,N-methyl morpholine, 2-ethyl-4-methylimidazole and1,8-diazabicyclo(5,4,0) undecene-7 (DBU); low-molecular-weight polyamideresins produced by the reactions between excessive quantities ofpolyamines and polybasic acids; and products of the reactions betweenexcessive quantities of polyamines and epoxy compounds. The silanolcondensing catalysts (O) useful for the present invention are notlimited to the above, and commonly used ones maybe used. These silanolcondensing catalysts may be used either individually or in combination.

Of these silanol condensing catalysts, organometallic compounds, and acombination of organometallic compound and amine-based compound are morepreferable, viewed from curability of the composition. The still morepreferable ones include organotin compounds, especially tetravalentones. A combination of a tetravalent organotin compound and a compound,as the (N) component, having both amino group (especially primary orsecondary) and hydrolyzable silicon group gives the cured productparticularly excellent in modulus of elasticity and strength.

The (O) component is incorporated preferably at 0.01 to 20 parts byweight per 100 parts by weight of the (A2) component, preferably 0.5 to10 parts by weight. At below 0.01 parts, the (A2) component containing areactive silicon group will have insufficient crosslinking reactivity.At above 20 parts, on the other hand, the adverse effects on adhesionand other properties are anticipated. Therefore, the content beyond theabove range is undesirable.

The epoxy resin curing agents (P) useful for the present inventioninclude primary or secondary amines, e.g., triethylenetetramine,tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperizine,menthenediamine, isophoronediamine, morpholine, piperizine,m-xylylenediamine, m-phenylenediamine, diaminodiphenylmethane anddiaminodiphenylsulfone; tertiary amines, e.g., trialkylamine,N-methylmorpholine, N,N′-dimethylpiperazine, pyridine, picoline,guanidine, diphenylguanidine, 1,8-diazabicyclo(5,4,0) undecene-7 (DBU),benzyldimethylamine, 2-(dimethylaminomethyl) phenol and2,4,6-tris(dimethylaminomethyl) phenol; organic acid salts of thesetertiary amines; imidazoles, e.g., 2-methylimidazole,2-ethyl-4-methylimidazole, 2-undecylimidazole and1-benzyl-2-methylimidazole; polyamides; dicyandiamides; borontrifluoride/amine complexes; carboxylic anhydrides, e.g., phthalicanhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride,endomethylene/tetrahydrophthalic anhydride, dodecylsuccinic anhydride,trimellitic anhydride, pyromellitic anhydride, chlorendic anhydride;alcohols; phenols; carboxylic acids; Lewis acids, e.g., borontrifluoride, phosphorus hexafluoride, aluminum trichloride and tintetrachloride; and the salts of these Lewis acids. The epoxy resinscuring agents (P) useful for the present invention are not limited tothe above, and commonly used ones maybe used. These epoxy resins curingagents may be used either individually or in combination. Of these epoxyresins curing agents, tertiary amines, organic salts thereof andimidazoles are more preferable, viewed from curability of thecomposition.

Desired content of the (P) component varies depending on its type andtype of the epoxy resin as the (K3) component. However, it isincorporated at a varying content in a range of 0.01 to 300 parts byweight per 100 parts by weight of the (K3) component for specificpurposes.

The method of preparing the curable resin composition containing the(A2), (K3), (N), (O) and (P) components is not limited. It may beprepared by the common method, e.g., kneading these components by, e.g.,a mixer, roll or kneader, or mixing them after dissolving each componentin an adequate solvent. Each component can be adequately combined withthe others to produce a one-liquid or two-liquid type composition.

The rubber composition (13) of the present invention may be adequatelyincorporated with one or more additives. The additives useful for thepresent invention include adhesion improver, property adjuster, storagestability improver, plasticizer, filler, aging inhibitor, ultravioletray absorber, metal deactivator, ozone-caused aging inhibitor, lightstabilizer, amine-based radical chaining inhibitor, phosphorus-basedperoxide decomposer, lubricant, pigment, and foaming agent.

The adhesion improvers useful for the present invention include commonlyused adhesives and others, other than the above-described epoxy resin(K3) and silane coupling agent (N). The concrete examples of theseadhesion improvers include phenolic resin, coumarone/indene resin, rosinester resin, terpene/phenol resin, α-methyl styrene/vinyl toluenecopolymer, polyethylmethyl styrene, alkyl titanates, and aromaticpolyisocyanate. The adhesion improver, when used, is incorporatedpreferably at about 1 to 50 parts by weight per 100 parts by weight ofthe (A2) component, more preferably about 5 to 30 parts by weight.

The storage stability improvers useful for the present invention includecompounds with silicon to which a hydrolyzable group is bonded, andesters of ortho-organic acids. The concrete examples of the storagestability improvers include methyltrimethoxy silane, methyltriethoxysilane, tetramethoxy silane, ethyltrimethoxy silane, dimethyldiethoxysilane, trimethylisobutoxy silane, trimethyl(n-butoxy) silane,n-butyltrimethoxy silane, and methyl orthoformate. The storage stabilityimprover, when used, is incorporated preferably at about 0.5 to 20 partsby weight per 100 parts by weight of the (A2) component, more preferablyabout 1 to 10 parts by weight.

The plasticizer useful for the present invention is also not limited,and any commonly used one may be used. Preferably, it should becompatible with each component for the rubber composition (13) of thepresent invention. The concrete examples of these plasticizers includehydrocarbon-based compounds, e.g., polybutene, hydrogenated polybutene,ethylene/α-olefin oligomer, α-methyl styrene oligomer, biphenyl,triphenyl, triaryl dimethane, alkylene triphenyl, liquid polybutadiene,hydrogenated liquid polybutadiene, alkyl diphenyl, partiallyhydrogenated ter-phenyl, paraffin oil, naphthene oil and atacticpolypropylene; parafin chlorides; phthalate esters, e.g., those ofdibutyl phthalate, diheptyl phthalate, di(2-ethylhexyl) phthalate, butylbenzyl phthalate and butyl phthalyl butyl glycolate; non-aromatic,dibasic acid esters, e.g., those of dioctyl adipate and dioctylcebacate; esters of polyalkylene glycol, e.g., those of diethyleneglycol benzoate and triethylene glycol dibenzoate; and

phosphate esters, e.g., those of tricresyl phosphate and tributylphosphate. They may be used either individually or in combination.

Of these, hydrocarbon-based compounds free of unsaturated group, e.g.,hydrogenated polybutene, hydrogenated liquid polybutadiene, paraffinoil, naphthene oil and atactic polypropylene, are more preferable forvarious reasons, e.g., high compatibility with each component for therubber composition (13) of the present invention, limited effects oncuring speed of the rubber composition, good resistance to weather ofthe cured product, and cheapness.

The plasticizer may be used in place of the solvent during the processof introducing a reactive silicon group into theethylene/α-olefin/non-conjugated polyene random copolymer rubber, forthe purposes of, e.g., adjusting reaction temperature and viscosity ofthe reaction system.

The plasticizer, when used, is incorporated preferably at about 10 to500 parts by weight per 100 parts by weight of the (A2) component, morepreferably about 20 to 300 parts by weight.

The concrete examples of the fillers include wood powder, pulp, cottonchips, asbestos, glass fibers, carbon fibers, mica, walnut shell powder,rice hull powder, graphite, diatomaceous earth, white clay, fumedsilica, settling silica, silicic anhydride, carbon black, calciumcarbonate, clay, talc, titanium oxide, magnesium carbonate, quartz, finealuminum powder, flint powder, and zinc powder. Of these, morepreferable ones are thixotropic fillers, e.g., settling silica, fumedsilica and carbon black; and calcium carbonate, titanium oxide and talc.The filler, when used, is incorporated preferably at about 10 to 500parts by weight per 100 parts by weight of the totaled (A2), (K3), (N),(O) and (P) components, more preferably about 20 to 300 parts by weight.

The aging inhibitors useful for the present invention include commonlyused known ones, e.g., sulfur-based ones, radical inhibitors andultraviolet ray absorbers.

The sulfur-based aging inhibitors useful for the present inventioninclude mercaptans, salts thereof, sulfides including sulfidecarboxylate esters and hindered phenol-based sulfides, polysulfides,dithiocarboxylates, thioureas, thiophosphates, sulfonium compounds,thioaldehydes, thioketones, mercaptals, mercaptols, monothio acids,polythio acids, thioamides, and sulfoxides. The concrete examples of thesulfur-based aging inhibitors include mercaptans, e.g.,2-mercaptobenzothiazole; salts of mercaptans, e.g., zinc salt of2-mercaptobenzothiazole; sulfides, e.g.,4,4′-thio-bis(3-methyl-6-t-butyl phenol),4,4′-thio-bis(2-methyl-6-t-butyl phenol),2,2′-thio-bis(4-methyl-6-t-butyl phenol),bis(3-methyl-4-hydroxy-5-t-butylbenzyl) sulfide, terephthaloyldi(2,6-dimethyl-4-t-butyl-3-hydroxybenzyl) sulfide, phenothiazine,2,2′-thio-bis(4-octyl phenol) nickel, dilauryl thiodipropionate,distearyl thiodipropionate, dimyristyl thiodipropionate, ditridecylthiodipropionate, distearylβ,β′-thiodibutyrate, lauryl-stearylthiodipropionate and 2,2-thio[diethyl-bis-3(3,5-di-t-butyl-4-hydroxyphenol)propionate]; polysulfides, e.g., 2-benzothiazole disulfide;dithiocarboxylates, e.g., zinc dibutyldithiocarbamate, zincdiethyldithiocarbamate, nickel dibutyldithiocarbamate, zincdi-n-butyldithiocarbamate, dibutyl ammonium dibutyldithiocarbamate, zincethyl-phenyl-dithiocarbamate and zinc dimethyldithiocarbamate;thioureas, e.g., 1-butyl-3-oxy-diethylene-2-thiourea,di-o-tolyl-thiourea and ethylene thiourea; and thiophosphates, e.g.,trilauryltrithiophosphate.

The above-described sulfur-based aging inhibitor preventsdecomposition/aging of the main chain under heating much moreefficiently than the other types for the rubber composition of thepresent invention, controlling the problems, e.g., residual surfacetackiness.

The radical inhibitors useful for the present invention includephenol-based ones, e.g., 2,2-methylene-bis(4-methyl-6-t-butyl phenol)and tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane; and amine-based ones, e.g., phenyl-β-naphthylamine,α-naphthylamine, N,N′-sec-butyl-p-phenylenediamine, phenothiazine andN,N′-diphenyl-p-phenylenediamine.

The ultraviolet ray absorbers useful for the present invention include2-(2′-hydroxy-3′,5′-di-t-butylphenyl) benzotriazole andbis(2,2,6,6-tetramethyl-4-piperidine) cebacate.

The aging inhibitor, when used, is incorporated at about 0.1 to 20 partsby weight per 100 parts by weight of the (A2) component, more preferablyabout 1 to 10 parts by weight.

The rubber composition (13) of the present invention can be prepared byuniformly kneading the components by a kneader, e.g., intermix mixer,planetary mixer, Banbury mixer, kneader or 2-roll unit.

The rubber composition (13) of the present invention is cured at roomtemperature to 200° C. for several minutes to several days, because itcan be cured quickly. It is particularly preferable to crosslink thecomposition with moisture in air at room temperature.

Uses of the Rubber Composition

The rubber composition (13) of the present invention can be suitablyused as sealants, and also as adhesives, tackifiers, paints, shapingmaterials, spray materials, casting rubber materials and foamingmaterials. When it is used for a sealant, it can be a one-liquid sealantcomposition which is quickly cured when exposed to moisture in air whilebeing applied to form a good rubber elastomer, because it can be keptstable for extended periods when stored in a closed condition, after thecuring catalyst is kneaded with the other components in a moisture-freecondition.

The rubber composition (13) of the present invention contains thecurable composition with the ethylene/α-olefin/non-conjugated polyenerandom copolymer rubber containing a hydrolyzable silyl group as thecomponent (A2), wherein the organic polymer (Z1) contains a hydrolyzablesilyl group represented by the above-described general formula (1) andessentially no unsaturated double bond in the main chain. It can besuitably used for electric/electronic device members, transportationmachines, and civil engineering/construction, medical and leisure areas,as described earlier.

The rubber composition (13) of the present invention can be used assealants, potting agents, coating materials or adhesives forelectric/electronic device members, transportation machines, and civilengineering/construction, and leisure areas.

The curable rubber composition (13) thus prepared can have a varyingcohesive force of the matrix by changing type and addition rate of thesilane coupling agent to control the layered structure of the curedproduct. As a result, it can give widely varying cured products, fromthe one having a low modulus of elasticity and high elongation, like theconventional cured product, to the one having a high modulus ofelasticity and tensile shear strength.

In other words, the curable rubber composition (13) of the presentinvention is highly adhesive, and can give not only the cured producthaving a low modulus of elasticity and high elongation but also the oneof improved cohesion force of the matrix, high in modulus of elasticityand tensile shear strength by changing addition rate of the silanecoupling agent. Moreover, it is high in curing speed, and excellent inresistance to light, when cured. Therefore, it can cover desiredmechanical characteristics by the simple procedure of changing additionrate of the silane coupling agent, and is particularly suitable foradhesive, sealant and tackifier agent.

Rubber Composition (14)

The rubber composition (14) of the present invention contains thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A2), an epoxy resin (K3), a silicon compound (Q)containing a functional group reactive with the epoxy group and thehydrolyzable silyl group in the molecule, and a silicon compound (R)containing at least two hydroxyl groups bonded to the silicon atom inthe molecule.

The rubber composition (14) of the present invention contains thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A2) preferably at 10% or more, more preferably at 20%or more, still more preferably at 30% or more.

The epoxy resins (K3) for the rubber composition (14) of the presentinvention include epichlorohydrin-bisphenol A type epoxy resins,epichlorohydrin-bisphenol F type epoxy resins, flame-retardant typeepoxy resins (e.g., glycidyl ethers of tetrabromophenol A type), novolactype epoxy resins, hydrogenated bisphenol A type epoxy resins, glycidylether type epoxy resins of bisphenol A type propylene oxide adduct;glycidyl ester type epoxy resins, e.g., diglycidyl-p-oxybenzoate,phthalate diglycidyl ester, tetrahydrophthalate diglycidyl ester,hexahydrophthalate diglycidyl ester, m-aminophenol-based epoxy resin,diaminodiphenylmethane-based epoxy resin, uretahne-modified epoxy resin,various types of alicyclic epoxy resin, N,N-diglycidylaniline,N,N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkyleneglycol diglycidyl ether, glycidyl ethers of polyhydric alcohols, e.g.,glycerin, hydantoin type epoxy resin, and epoxidized unsaturatedpolymers, e.g., oil-derived resins. The epoxy resins (K3) useful for thepresent invention are not limited to the above, and commonly used epoxyresins may be used.

Of these epoxy resins, the more preferable ones include those having atleast two epoxy groups, because they are highly reactive for the curingand produce the network structures more easily. Still more preferableones include bisphenol A type epoxy resins, phthalate ester-baseddiglycidyl esters, and novolac type epoxy resins.

In the present invention, a curing agent which promotes curing of theepoxy resin (K3) may be used. The epoxy resin curing agents useful forthe present invention include the commonly used agents for curing epoxyresins. These curing agents include amines, e.g., triethylenetetramine,tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine,m-xylylenediamine, m-phenylenediamine, diaminodiphenylmethane,diaminodiphenylsulfone, isophoronediamine,2,4,6-tris(dimethylaminomethyl) phenol; salts of tertiary amines;polyamide resins; imidazoles; dicyandiamides; boron trifluoridecomplexes; carboxylic anhydrides, e.g., phthalic anhydride,hexahydrophthalic anhydride, tetrahydrophthalic anhydride,endomethylene/tetrahydrophthalic anhydride, dodecylsuccinic anhydride,pyromellitic anhydride and chlorendic anhydride; alcohols; phenols; andcarboxylic acids.

Desired content of the curing agent varies depending on its type andtype of the epoxy resin. However, it is incorporated at a varyingcontent in a range of 0.1 to 300 parts by weight per 100 parts by weightof the (K3) component for specific purposes.

The (Q) component for the present invention is a silicon compoundcontaining a functional group reactive with the epoxy group andhydrolyzable silyl group in the molecule.

The functional groups in the silicon compound, reactive with an epoxygroup include primary, secondary and tertiary amino, mercapto, epoxy andcarboxyl. As the hydrolyzable silyl groups, any of those for the (A2)component may be used. Of these, the more preferable ones includealkoxysilyl, because of its easiness of handling, among others.

The concrete examples of these silicon compounds includeamino-containing silanes, e.g., γ-aminopropyltrimethoxysilane,γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane,γ-(2-aminoethyl) aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyltriethoxysilane, γ-ureidopropyltriethoxysilane,N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane andγ-anilinopropyltrimethoxysilane; mercapto-containing silanes, e g.,γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane,γ-mercaptopropylmethyldimethoxysilane andγ-mercaptopropylmethyldiethoxysilane; epoxy bond-containing silanes,e.g., γ-glycidoxypropyltrimethoxysilane,γ-glycidoxypropylmethyldimethoxysilane,γ-glycidoxypropyltriethoxysilane,β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; and carboxyls, e.g.,β-carboxylethyltriethoxysilane,β-carboxylethylphenylbis(2-methoxyethoxy) silane andN-β-(N-carboxymethylaminoethyl)-γ-aminopropyltrimethoxysilane. Thesesilicon compounds (Q) may be used either individually or in combination.

The (R) component for the present invention is a silicon compoundcontaining at least two hydroxyl groups, preferably 2 to 4, bonded tothe silicon atom in the molecule.

These silicon compounds include polydimethylsiloxane having silanolgroup at the terminal, polydiphenylsiloxane having silanol group at theterminal, polydimethyldiphenylsiloxane having diphenylsilanol group atthe terminal, diphenylsilanediol, bis(hydroxydimethylsilyl)benzene,polytetramethyl-p-silphenylenesiloxane, organosilicon compounds havinghydroxyl group at the terminal, e.g., silicone varnish, andorganopolysiloxanes.

The (A2) component whose hydrolyzable group in the rubber-based organicpolymer is converted into silanol group can be also used as the (R)component. The concrete examples of these polymers include polypropyleneoxide having dimethylsilanol group at the terminal of the molecule.Content of the silanol-containing rubber-based polymer depends on itsmolecular weight and silanol content. However, generally speaking, it ispreferably incorporated at 10 to 100 parts by weight per 100 parts byweight of the (A2) component. Of these compounds, more preferable onesinclude diphenylsilanediol, which has a low molecular weight per onehydroxyl group bonded to the silicon atom, and itself having nopossibility of self-condensing. These compounds may be used eitherindividually or in combination.

The curable composition (14) is prepared by incorporating, as theeffective ingredients, the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber as the(A2) component, an epoxy resin as the (K3) component, and siliconcompounds as the (Q) and (R) components.

The curable composition (14) can be stably cured even when there is nota sufficient quantity of moisture in the ambient atmosphere, because itcan be cured by the actions of the silanol group in the (R) componentcontaining at least two hydroxyl groups bonded to the silicon atom inthe molecule, when it is included in the composition comprising the(A2), (K3) and (Q) components. The composition (14) of the presentinvention therefore is useful, even when applied under the conditionswhere moisture is difficult to enter the system, particularly useful fora sealant, an adhesive and a potting agent.

The condensing reaction does proceed in the composition comprising the(A2), (K3) and (Q) components after the hydrolyzable silyl group in the(A2) and (Q) components is partly hydrolyzed. In the composition furtherincorporated with the (R) component, on the other hand, the condensingreaction is considered to proceed without undergoing the hydrolysisstep, in the presence of the silanol group in the (R) component.

The ratio of the (K3) component to the (A2) component, i.e., (A2)/(K3)ratio, is preferably in a range of 100/1 to 100/200 by weight. The curedproduct tends to have an insufficient strength that above 100/1, andinsufficient rubber-like properties at below 100/200. The parts byweight of the (K3) component per 100 parts by weight of the (A2)component is more preferably 10 to 120/100, still more preferably 20 to100/100, when the rubber-like properties of the cured product are to besufficiently manifested, and its strength is to be sufficientlyimproved, although the preferable ratio varies depending on purposes ofthe curable composition.

The silicon compound as the (Q) component is incorporated preferably atan ((A2)+(K3) components)/(Q) component ratio of 100/0.1 to 100/20 byweight, more preferably 100/0.2 to 100/10. The cured product tends tohave an insufficient strength at above 100/0.1, and insufficientrubber-like properties at below 100/20.

The silicon compound as the (R) component is incorporated preferably atan (A2) component/(R) component ratio of 100/0.1 to 100/100 by weight,more preferably 100/0.2 to 100/50. The cured product tends to beinfluenced to moisture in the ambient atmosphere and lose stablecharacteristics at above 100/0.1, and insufficient rubber-likeproperties at below 100/100.

The method of preparing the curable rubber composition (14) containingthe (A2), (K3), (Q) and (R) components is not limited. It may beprepared by the common method, e.g., kneading these components by, e.g.,a mixer, roll or kneader at normal temperature or elevated temperature,or mixing them after dissolving each component in a small quantity of asuitable solvent. These components can be adequately combined with eachother to produce a one-liquid or a two-liquid type composition.

The rubber composition (14) of the present invention may be adequatelyincorporated with one or more additives. The additives useful for thepresent invention include adhesion improver, property adjuster, storagestability improver, plasticizer, filler, aging inhibitor, ultravioletray absorber, metal deactivator, ozone-caused aging inhibitor, lightstabilizer, amine-based radical chaining inhibitor, phosphorus-basedperoxide decomposer, lubricant, pigment, and foaming agent.

The adhesion improvers useful for the present invention include commonlyused adhesives and others, other than the above-described epoxy resin asthe (K3) components and silicon compounds as the (Q) and (R) components.

The concrete examples of these adhesion improvers include phenolicresin, coumarone/indene resin, rosin ester resin, terpene/phenol resin,α-methyl styrene/vinyl toluene copolymer, polyethylmethyl styrene, alkyltitanates, and aromatic polyisocyanate. The adhesion improver, whenused, is incorporated preferably at about 1 to 50 parts by weight per100 parts by weight of the (A2) component, more preferably about 5 to 30parts by weight.

The storage stability improvers useful for the present invention includecompounds with silicon to which a hydrolyzable group is bonded, andesters of ortho-organic acids.

The concrete examples of the storage stability improvers includemethyltrimethoxy silane, methyltriethoxy silane, tetramethoxy silane,ethyltrimethoxy silane, dimethyldiethoxy silane, trimethylisobutoxysilane, trimethyl (n-butoxy) silane, n-butyltrimethoxy silane, andmethyl orthoformate. The storage stability improver, when used, isincorporated preferably at about 0.5 to 20 parts by weight per 100 partsby weight of the (A2) component, more preferably about 1 to 10 parts.

The plasticizer useful for the present invention is also not limited,and any commonly used one may be used. Preferably, it should becompatible with each component for the rubber composition (14) of thepresent invention.

The concrete examples of these plasticizers include hydrocarbon-basedcompounds, e.g., polybutene, hydrogenated polybutene, ethylene/α-olefinoligomer, α-methyl styrene oligomer, biphenyl, triphenyl, triaryldimethane, alkylene triphenyl, liquid polybutadiene, hydrogenated liquidpolybutadiene, alkyl diphenyl, partially hydrogenated ter-phenyl,paraffin oil, naphthene oil and atactic polypropylene; parafinchlorides; phthalate esters, e.g., those of dibutyl phthalate, diheptylphthalate, di(2-ethylhexyl) phthalate, butyl benzyl phthalate and butylphthalyl butyl glycolate; non-aromatic, dibasic acid esters, e.g., thoseof dioctyl adipate and dioctyl cebacate; esters of polyalkylene glycol,e.g., those of diethylene glycol benzoate and triethylene glycoldibenzoate; and phosphate esters, e.g., those of tricresyl phosphate andtributyl phosphate. They may be used either individually or incombination.

Of these, hydrocarbon-based compounds free of unsaturated group, e.g.,hydrogenated polybutene, hydrogenated liquid polybutadiene, paraffinoil, naphthene oil and atactic polypropylene, are more preferable forvarious reasons, e.g., high compatibility with each component for therubber composition (14) of the present invention, limited effects oncuring speed of the rubber composition, good resistance to weather ofthe cured product, and cheapness.

The plasticizer may be used in place of the solvent during the processof introducing a reactive silicon group into theethylene/α-olefin/non-conjugated polyene random copolymer rubber, forthe purposes of, e.g., adjusting reaction temperature and viscosity ofthe reaction system.

The plasticizer, when used, is incorporated preferably at about 10 to500 parts by weight per 100 parts by weight of the (A2) component, morepreferably about 20 to 300 parts by weight.

The concrete examples of the fillers include wood powder, pulp, cottonchips, asbestos, glass fibers, carbon fibers, mica, walnut shell powder,rice hull powder, graphite, diatomaceous earth, white clay, fumedsilica, settling silica, silicic anhydride, carbon black, calciumcarbonate, clay, talc, titanium oxide, magnesium carbonate, quartz, finealuminum powder, flint powder, and zinc powder. Of these, morepreferable ones are thixotropic fillers, e.g., settling silica, fumedsilica and carbon black; and calcium carbonate, titanium oxide and talc.The filler, when used, is incorporated preferably at about 10 to 500parts by weight per 100 parts by weight of the totaled (A2), K3), (Q)and (R) components, more preferably about 20 to 300 parts by weight.

The aging inhibitors useful for the present invention include commonlyused known ones, e.g., sulfur-based ones, radical inhibitors andultraviolet ray absorbers.

The sulfur-based aging inhibitors useful for the present inventioninclude mercaptans, salts thereof, sulfides including sulfidecarboxylate esters and hindered phenol-based sulfides, polysulfides,dithiocarboxylates, thioureas, thiophosphates, sulfonium compounds,thioaldehydes, thioketones, mercaptals, mercaptols, monothio acids,polythio acids, thioamides, and sulfoxides.

The concrete examples of the sulfur-based aging inhibitors includemercaptans, e.g., 2-mercaptobenzothiazole; salts of mercaptans, e.g.,zinc salt of 2-mercaptobenzothiazole; sulfides, e.g.,4,4′-thio-bis(3-methyl-6-t-butyl phenol),4,4′-thio-bis(2-methyl-6-t-butyl phenol),2,2′-thio-bis(4-methyl-6-t-butyl phenol),bis(3-methyl-4-hydroxy-5-t-butylbenzyl) sulfide, terephthaloyldi(2,6-dimethyl-4-t-butyl-3-hydroxybenzyl) sulfide, phenothiazine,2,2′-thio-bis(4-octyl phenol) nickel, dilauryl thiodipropionate,distearyl thiodipropionate, dimyristyl thiodipropionate, ditridecylthiodipropionate, distearyl β,β′-thiodibutyrate, lauryl-stearylthiodipropionate and 2,2-thio[diethyl-bis-3(3,5-di-t-butyl-4-hydroxyphenol)propionate]; polysulfides, e.g., 2-benzothiazole disulfide;dithiocarboxylates, e.g., zinc dibutyldithiocarbamate, zincdiethyldithiocarbamate, nickel dibutyldithiocarbamate, zincdi-n-butyldithiocarbamate, dibutyl ammonium dibutyldithiocarbamate, zincethyl-phenyl-dithiocarbamate and zinc dimethyldithiocarbamate;thioureas, e.g., 1-butyl-3-oxy-diethylene-2-thiourea,di-o-tolyl-thiourea and ethylene thiourea; and thiophosphates, e.g.,trilauryltrithiophosphate.

The above-described sulfur-based aging inhibitor preventsdecomposition/aging of the main chain under heating much moreefficiently than the other types for the rubber composition of thepresent invention, controlling the problems, e.g., residual surfacetackiness.

The radical inhibitors useful for the present invention includephenol-based ones, e.g., 2,2-methylene-bis(4-methyl-6-t-butyl phenol)and tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane; and amine-based ones, e.g., phenyl-β-naphthylamine,α-naphthylamine, N,N′-sec-butyl-p-phenylenediamine, phenothiazine andN,N′-diphenyl-p-phenylenediamine.

The ultraviolet ray absorbers useful for the present invention include2-(2′-hydroxy-3′,5′-di-t-butylphenyl)benzotriazole andbis(2,2,6,6-tetramethyl-4-piperidine)cebacate.

The aging inhibitor, when used, is incorporated at about 0.1 to 20 partsby weight per 100 parts by weight of the (A2) component, more preferablyabout 1 to 10 parts by weight.

The rubber composition (14) of the present invention can be prepared byuniformly kneading the components by a kneader, e.g., intermix mixer,planetary mixer, Banbury mixer, kneader or 2-roll unit.

The rubber composition (14) of the present invention is cured at roomtemperature to 200° C. for several minutes to several days, because itcan be cured quickly. It is particularly preferable to crosslink thecomposition with moisture in air at room temperature.

Uses of the Rubber Composition (14)

The rubber composition (14) of the present invention can be suitablyused as a sealant, and also as adhesives, tackifiers, paints, shapingmaterials, spray materials, casting rubber materials and foamingmaterials.

When it is used for a sealant, it can be a one-liquid sealantcomposition which is quickly cured when exposed to moisture in air whilebeing applied to form a good rubber elastomer, because it can be keptstable for extended periods when stored in a closed condition, after thecuring catalyst is kneaded with the other components in a moisture-freecondition.

The rubber composition (14) of the present invention contains thecurable composition with the ethylene/α-olefin/non-conjugated polyenerandom copolymer rubber containing a hydrolyzable silyl group as thecomponent (A2), wherein the organic polymer (Z1) contains a hydrolyzablesilyl group represented by the above-described general formula (1) andessentially no unsaturated double bond in the main chain. It can besuitably used for electric/electronic device members, transportationmachines, and civil engineering/construction, medical and leisure areas,as described earlier.

The rubber composition (14) of the present invention can be used assealants, potting agents, coating materials or adhesives forelectric/electronic device members, transportation machines, and civilengineering/construction, and leisure areas.

The curable rubber composition (14) of the present invention can becured even at low temperature around room temperature, and quickly curedby increasing temperature to about 100 to 150° C. Therefore, it can becured and used over a wide temperature range from low to hightemperature, depending on specific purposes. The curable rubbercomposition (14) of the present invention can be cured at roomtemperature to give the product of high strength, when a combination ofepoxy resin/epoxy resin curing agent is selected from those curable atroom temperature. The cured product from the composition without solventcan be easily molded when a liquid-type epoxy resin is used.

The method of molding the curable rubber composition (14) of the presentinvention is not limited. However, the method is preferably selectedfrom those commonly used for solid rubber, e.g., natural rubber, and forrubber-based liquid polymer, e.g., polyurethane. Such a molding methodcan give the cured products, e.g., molded rubber and rubber-like foamedproducts, of improved properties, e.g., strength. The composition (14)can be also suitably used for rubber-based adhesives, sealants,tackifiers and the like. In particular, it can give a rubber-basedadhesive high both in releasing strength and shear strength, when the(A2)/(K3) ratio is set at 100/20 to 100/100 by weight.

The curable rubber composition (14) of the present invention can bestably cured irrespective of atmosphere in which it is cured, even inthe absence of a sufficient quantity of moisture, and can solve theproblem of low strength involved in the rubber-based cured producthaving a hydrolyzable silyl group. It has other advantages of highhardness, and improved resistance of the cured product to weather.

Rubber Composition (15)

The rubber composition (14) of the present invention contains thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A2), calcium carbonate (L1), and talc (L2). The rubbercomposition (15) of the present invention contains the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A2)preferably at 10% or more, more preferably at 20% or more, still morepreferably at 30% or more. The rubber composition (15) of the presentinvention is incorporated with two types of inorganic fillers (L),calcium carbonate (L1) and talc (L2), to simultaneously secure goodworkability (spinning property) of the composition and good mechanicalproperties (in particular hardness) of its cured product.

Calcium carbonate as the (L1) component falls into two generalcategories, limestone powder produced by mechanicallycrushing/processing natural chalk, limestone, marble or the like, andlight calcium carbonate produced by a wet process involving chemicalreactions from limestone or the like as the stock material, specificallyreferred to as colloidal calcium carbonate, when it is produced undercontrolled conditions into ultrafine colloidal particles. Of thesecalcium carbonate types, the preferable ones are limestone powder forits low cost, and colloidal calcium carbonate for its notable effect ofimproving workability (spinning property) of the composition. These maybe used either individually or in combination.

Limestone powder may be crushed either by a dry or wet method, thelatter being unsuitable for the present invention, because its productfrequently deteriorates storage stability of the rubber composition (15)of the present invention. Calcium carbonate as the component (L1) forthe present invention is more preferably surface-treated one with asurface treating agent. Surface treatment of calcium carbonate as thecomponent (L1) improves adhesion properties of the composition (15) ofthe present invention and further improves its effect of improvingworkability.

The surface treating agents useful for the present invention includeorganic compounds, e.g., fatty acids, fatty acid soaps and fatty acidesters; various types of surfactants; ad coupling agents, e.g., silane-and titanate-based ones.

The concrete examples of these organic compounds include fatty acids,e.g., caproic, capryl, pelargonic, capric, undecanic, lauric, myristic,palmitic, stearic, behenic and oleic acids; sodium and potassium saltsthereof; and alkyl esters thereof.

The concrete examples of the surfactants useful for the presentinvention include polyoxyethylene alkyl ether sulfate esters andlong-chain alcohol sulfate esters; sodium and potassium salts thereof assulfate ester type anionic surfactants; alkyl benzenesulfonates, alkylnaphthalenesulfonates, paraffin sulfonates, α-olefin sulfonates andalkyl sulfosuccinates; and sodium and potassium salts thereof assulonate type anionic surfactants.

Calcium carbonate is treated with 0.1 to 20% by weight of the surfacetreating agent, based on the calcium carbonate, more preferably with 1to 5% by weight of the agent. The agent may not bring a sufficienteffect of improving workability, adhesion and resistance to weather atbelow 0.1%, and deteriorate storage stability of the curable compositionat above 20%.

The (L1) component is preferably incorporated at 5 to 500 parts byweight per 100 parts of the (A2) component, more preferably 20 to 350parts, still more preferably 40 to 200 parts by weight. The componentmay not bring a sufficient effect of improving workability (spinningproperty) of the rubber composition at below 5 parts, and deteriorateits adhesion at above 500 parts. These compounds maybe used eitherindividually or in combination for the (L1) component.

Talc as the (L2) component is an inorganic filler obtained bymechanically crushing/processing/classifying the stock material known astalcum, and comprises magnesium silicate (3MgO.4SiO₂.H₂O) as the majoringredient. Talc as the (L2) component for the present invention may beuntreated or surface-treated with a surface treating agent. Whensurface-treated, it improves storage stability of the rubber composition(15) of the present invention.

The surface treating agents useful for the (L2) component can be thesame as those for the (L1) component.

The (L2) component is preferably incorporated at 5 to 300 parts byweight per 100 parts of the (A2) component, more preferably 20 to 200parts, still more preferably 40 to 150 parts by weight. The componentmay not bring a sufficient effect of improving mechanicalcharacteristics of the cured product from the composition at below 5parts, and deteriorate its adhesion at above 300 parts. These compoundsmay be used either individually or in combination for the (L2)component.

The rubber composition (15) of the present invention may be incorporatedwith various types of fillers, in addition to calcium carbonate as the(L1) component and talc as the (L2) component. The concrete examples ofthe fillers include reinforcing fillers, e.g., fumed silica, settlingsilica, silicic anhydride, silicic hydride and carbon black; fillers,e.g., diatomaceous earth, fired clay, clay, talc, titanium oxide,bentonite, organic bentonite, ferric oxide, zinc oxide, activated zincwhite; fibrous fillers, e.g., glass fibers or filaments.

The rubber composition (15) of the present invention may be incorporatedwith a silane coupling agent. This agent improves adhesion strength ofthe cured silyl-containing ethylene/α-olefin/non-conjugated polyenerandom copolymer rubber (A2) to the base material and other objects. Theagent is a compound which has a group containing the silicon atom towhich a hydrolyzable group is bonded (hereinafter referred to ashydrolyzable silicon group) and one or more other functional groups. Thehydrolyzable silicon groups useful for the present invention includethose represented by the above-described general formula (I) in which Xis a hydrolyzable group. The concrete examples include those describedearlier as the hydrolyzable groups, of which methoxy and ethoxy are morepreferable viewed from hydrolysis speed. The compound preferably has 2or more hydrolyzable groups, still more preferably 3 or more.

The functional groups useful for the present invention, other than thehydrolyzable silicon groups, include a primary, secondary and tertiaryamino, epoxy, carboxyl, vinyl, isocyanate, isocyanurate, and halogen. Ofthese, primary, secondary or tertiary amino, mercapto, epoxy, isocyanateand isocyanurate are more preferable, and isocyanate and epoxy are stillmore preferable.

The hydrolyzable silicon group is preferably bonded to the otherfunctional group via a hydrocarbon group, e.g., alkylene or arylene,although not limited thereto.

The silane coupling agent has a molecular weight of 500 or less,particularly preferably 300 or less.

The silane coupling agents useful for the present invention includeamino-containing silanes, e.g., γ-aminopropyltrimethoxysilane,γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane,γ-aminopropylmethyldiethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropyltriethoxysilane,γ-(2-aminoethyl)aminopropyltriethoxysilane,γ-(2-aminoethyl)aminopropylmethyldiethoxysilane,γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane,N-benzyl-γ-aminopropyltrimethoxysilane andN-vinylbenzyl-γ-aminopropyltriethoxysilane; mercapto-containing silanes,e.g., γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane,γ-mercaptopropylmethyldimethoxysilane andγ-mercaptopropylmethyldiethoxysilane; epoxy-containing silanes, e.g.,γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane,γ-glycidoxypropylmethyldimethoxysilane,γ-glycidoxypropylmethyldiethoxysilane,β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane andβ-(3,4-epoxycyclohexyl)ethyltriethoxysilane; carboxysilanes, e.g.,β-carboxyethyltriethoxysilane,β-carboxyethylphenylbis(2-methoxyethoxy)silane andN-β-(carboxymethyl)aminoethyl-γ-aminopropyltrimethoxysilane; vinyl typeunsaturated group-containing silanes; e.g., vinyltrimethoxysilane,vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane andγ-acryloyloxypropylmethyltriethoxysilane; halogen-containing silanes,e.g., γ-chloropropyltrimethoxysilane; silane isocyanurates, e.g.,tris(trimethoxysilyl)isocyanurate; and isocyanate-containing silanes,e.g., γ-isocyanate propyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-isocyanate propylmethyldiethoxysilane andγ-isocyanate propylmethyldimethoxysilane.

Moreover, the modifications of these compounds as their derivatives arealso useful as the silane coupling agents. These compounds includeamino-modified silyl polymers, silylated amino polymers, unsaturatedaminosilane complexes, block isocyanate silanes, phenylamino-longchain-alkyl silanes, aminosilylated silicone and silylated polyesters.

The silane coupling agent is incorporated at 0.1 to 20 parts by weightper 100 parts by weight of the (A2) component, particularly preferably0.5 to 10 parts. These silane coupling agents may be used eitherindividually or in combination.

The rubber composition (15) of the present invention may be incorporatedwith a tackifier, other than a silane coupling agent.

The rubber composition (15) of the present invention is preferablyincorporated with a curing catalyst which promotes the silanolcondensation.

Widely varying known curing catalysts may be used for the presentinvention. The concrete examples of these catalysts useful for thepresent invention include titanate esters, e.g., those of tetrabutyltitanate and tetrapropyl titanate; tin carboxylates, e.g., dibutyl tindilaurate, dibutyl tin maleate, dibutyl tin diacetate, tin octylate andtin naphthenate; product of the reaction between dibutyl tin oxide andphthalate ester; dibutyl tin diacetylacetonate; organoaluminumcompounds, e.g., aluminum trisacetylacetonate, aluminumtrisethylacetoacetate and diisopropoxy aluminum ethylacetoacetate;chelate compounds, e.g., zirconium tetraacetylacetonate and titaniumtetraacetylacetonate; lead octylate; amine-based compounds, and salts ofthese compounds and carboxylates, e.g., butylamine, octylamine,dibutylamine, monoethanolamine, diethanolamine, triethanolamine,diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine,benzylamine, diethylaminopropylamine, xylylenediamine,triethylenediamine, guanidine, diphenylguanidine,2,4,6-tris(dimethylaminomethyl)phenol, morpholine, N-methyl morpholine,2-ethyl-4-methylimidazole and 1,8-diazabicyclo(5,4,0) undecene-7 (DBU);low-molecular-weight polyamide resins produced by the reactions betweenexcessive quantities of polyamines and polybasic acids; products of thereactions between excessive quantities of polyamines and epoxycompounds; and known silanol condensing catalysts, e.g., silane couplingagents containing amino group (e.g., γ-aminopropyl trimethoxy silane andN-(β-aminoethyl)aminopropylmethyldimethoxy silane); and other knowncatalysts, acidic or basic. These compounds may be used eitherindividually or in combination.

The curing catalyst, when used, is incorporated normally at around 0.1to 20 parts by weight per 100 parts by weight of the (A2) component,preferably around 1 to 10 parts by weight. An excessively low content ofthe catalyst is undesirable, because it may result in slow curing speedof the rubber composition product. On the other hand, an excessivelyhigh content of the catalyst is also undesirable, because it maydeteriorate the tensile-related characteristics of the cured product.

The rubber composition (15) of the present invention may be adequatelyincorporated with one or more additives. The additives useful for thepresent invention include adhesion improver, property adjuster, storagestability improver, plasticizer, aging inhibitor, ultraviolet rayabsorber, metal deactivator, ozone-caused aging inhibitor, lightstabilizer, amine-based radical chaining inhibitor, phosphorus-basedperoxide decomposer, lubricant, pigment, and foaming agent.

The adhesion improvers useful for the present invention include commonlyused adhesives and others, except a silane coupling agent.

The concrete examples of these adhesion improvers include phenolicresin, epoxy resin, coumarone/indene resin, rosin ester resin,terpene/phenol resin, α-methyl styrene/vinyl toluene copolymer,polyethylmethyl styrene, alkyl titanates, and aromatic polyisocyanate.The adhesion improver, when used, is incorporated preferably at about 1to 50 parts by weight per 100 parts by weight of the (A2) component,more preferably about 5 to 30 parts by weight.

The storage stability improvers useful for the present invention includecompounds with silicon to which a hydrolyzable group is bonded, andesters of ortho-organic acids.

The concrete examples of the storage stability improvers includemethyltrimethoxy silane, methyltriethoxy silane, tetramethoxy silane,ethyltrimethoxy silane, dimethyldiethoxy silane, trimethylisobutoxysilane, trimethyl(n-butoxy) silane, n-butyltrimethoxy silane, and methylorthoformate. The storage stability improver, when used, is incorporatedpreferably at about 0.5 to 20 parts by weight per 100 parts by weight ofthe (A2) component, more preferably about 1 to 10 parts.

The plasticizer useful for the present invention is also not limited,and any commonly used one may be used. Preferably, it should becompatible with each component for the rubber composition (15) of thepresent invention.

The concrete examples of these plasticizers include hydrocarbon-basedcompounds, e.g., polybutene, hydrogenated polybutene, ethylene/α-olefinoligomer, α-methyl styrene oligomer, biphenyl, triphenyl, triaryldimethane, alkylene triphenyl, liquid polybutadiene, hydrogenated liquidpolybutadiene, alkyl diphenyl, partially hydrogenated ter-phenyl,paraffin oil, naphthene oil and atactic polypropylene; parafinchlorides; phthalate esters, e.g., those of dibutyl phthalate, diheptylphthalate, di(2-ethylhexyl)pthalate, butyl benzyl phthalate and butylphthalyl butyl glycolate; non-aromatic, dibasic acid esters, e.g., thoseof dioctyl adipate and dioctyl cebacate; esters of polyalkylene glycol,e.g., those of diethylene glycol benzoate and triethylene glycoldibenzoate; and phosphate esters, e.g., those of tricresyl phosphate andtributyl phosphate. They may be used either individually or incombination.

Of these, hydrocarbon-based compounds free of unsaturated group, e.g.,hydrogenated polybutene, hydrogenated liquid polybutadiene, paraffinoil, naphthene oil and atactic polypropylene, are more preferable forvarious reasons, e.g., high compatibility with each component for therubber composition (15) of the present invention, limited effects oncuring speed of the rubber composition, good resistance to weather ofthe cured product, and cheapness.

The plasticizer may be used in place of the solvent during the processof introducing a reactive silicon group into theethylene/α-olefin/non-conjugated polyene random copolymer rubber, forthe purposes of, e.g., adjusting reaction temperature and viscosity ofthe reaction system.

The plasticizer, when used, is incorporated preferably at about 10 to500 parts by weight per 100 parts by weight of the (A2) component, morepreferably about 20 to 300 parts by weight.

The aging inhibitors useful for the present invention include commonlyused known ones, e.g., sulfur-based ones, radical inhibitors andultraviolet ray absorbers.

The sulfur-based aging inhibitors useful for the present inventioninclude mercaptans, salts thereof, sulfides including sulfidecarboxylate esters and hindered phenol-based sulfides, polysulfides,dithiocarboxylates, thioureas, thiophosphates, sulfonium compounds,thioaldehydes, thioketones, mercaptals, mercaptols, monothio acids,polythio acids, thioamides, and sulfoxides.

The concrete examples of the sulfur-based aging inhibitors includemercaptans, e.g., 2-mercaptobenzothiazole; salts of mercaptans, e.g.,zinc salt of 2-mercaptobenzothiazole; sulfides, e.g.,4,4′-thio-bis(3-methyl-6-t-butyl phenol),4,4′-thio-bis(2-methyl-6-t-butyl phenol),2,2′-thio-bis(4-methyl-6-t-butyl phenol),bis(3-methyl-4-hydroxy-5-t-butylbenzyl)sulfide, terephthaloyldi(2,6-dimethyl-4-t-butyl-3-hydroxybenzyl)sulfide, phenothiazine,2,2′-thio-bis (4-octyl phenol)nickel, dilauryl thiodipropionate,distearyl thiodipropionate, dimyristyl thiodipropionate, ditridecylthiodipropionate, distearylβ,β′-thiodibutyrate, lauryl-stearylthiodipropionate and 2,2-thio[diethyl-bis-3(3,5-di-t-butyl-4-hydroxyphenol)propionate]; polysulfides, e.g., 2-benzothiazole disulfide;dithiocarboxylates, e.g., zinc dibutyldithiocarbamate, zincdiethyldithiocarbamate, nickel dibutyldithiocarbamate, zincdi-n-butyldithiocarbamate, dibutyl ammonium dibutyldithiocarbamate, zincethyl-phenyl-dithiocarbamate and zinc dimethyldithiocarbamate;thioureas, e.g., 1-butyl-3-oxy-diethylene-2-thiourea,di-o-tolyl-thiourea and ethylene thiourea; and thiophosphates, e.g.,trilauryltrithiophosphate.

The above-described sulfur-based aging inhibitor preventsdecomposition/aging of the main chain under heating much moreefficiently than the other types for the rubber composition of thepresent invention, controlling the problems, e.g., residual surfacetackiness.

The radical inhibitors useful for the present invention includephenol-based ones, e.g., 2,2′-methylene-bis(4-methyl-6-t-butyl phenol)and tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane; and amine-based ones, e.g., phenyl-β-naphthylamine,α-naphthylamine, N,N′-sec-butyl-p-phenylenediamine, phenothiazine andN,N′-diphenyl-p-phenylenediamine.

The ultraviolet ray absorbers useful for the present invention include2-(2′-hydroxy-3′,5′-di-t-butylphenyl)benzotriazole andbis(2,2,6,6-tetramethyl-4-piperidine)cebacate.

The aging inhibitor, when used, is incorporated at about 0.1 to 20 partsby weight per 100 parts by weight of the (A2) component, more preferablyabout 1 to 10 parts by weight.

The effect of combining calcium carbonate as the (L1) component and talcas the (L2) component for the present invention is also observed, evenwhen it is further incorporated with the various additives describedabove. More concretely, the curable rubber composition (15) of thepresent invention, when used as elastomer sealants for constructionworks, or sealants for laminated glass, SSG construction method, orrust-preventive or water-proof of edges (cut sections) of wired orlaminated glass, will have still improved workability (spinningproperty) and mechanical characteristics (hardness).

The curable composition (15) of the present invention can be prepared byuniformly kneading the components by a kneader, e.g., intermix mixer,planetary mixer, Banbury mixer, kneader or 2-roll unit.

The curable composition (15) of the present invention is cured at roomtemperature to 200° C. for several minutes to several days, because itcan be cured quickly. It is particularly preferable to crosslink thecomposition with moisture in air at room temperature.

Rubber Composition (15) and its Uses

The rubber composition (15) of the present invention contains thecurable composition with the ethylene/α-olefin/non-conjugated polyenerandom copolymer rubber containing a reactive silicon group as thecomponent (A2), as is the case with the rubber composition (11). Moreconcretely, the rubber composition (15) of the present inventioncontains the organic polymer (Z1), calcium carbonate (L1) and talc (L2),wherein the (Z1) component contains a hydrolyzable silyl grouprepresented by the above-described general formula (1) and essentiallyno unsaturated double bond in the main chain. It can be suitably usedfor electric/electronic device members, transportation machines, andcivil engineering/construction, medical and leisure areas, as describedearlier.

The curable rubber composition (15) of the present invention can be usedas sealants, potting agents, coating materials or adhesives forelectric/electronic device members, transportation machines, and civilengineering/construction, and leisure areas.

Curable Composition (16)

The curable composition (16) of the present invention contains (a) thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1), (b) a nickel-containing light stabilizer (S) and(c) a silane coupling agent (T).

The curable composition (16) of the present invention contains thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1) preferably at 10% or more, more preferably at 20%or more, still more preferably at 30% or more.

The curable composition (16) of the present invention exhibits excellentcharacteristics with respect to curing speed and resistance to weather,which is mainly derived from the ethylene/α-olefin/non-conjugatedpolyene random copolymer rubber (A1) containing the hydrolyzable silylgroup.

Nickel-containing Light Stabilizer (S)

The present invention uses a light stabilizer containing atomic nickel(S) as the light stabilizer. The commercial nickel-based lightstabilizers can be generally used for the present invention as thestabilizer (S).

The concrete examples of the light stabilizers include nickeldithiocarbamates, e.g., nickel dimethyldithiocarbamate, nickeldiethyldithiocarbamate and nickel dibutyldithiocarbamate; nickelcomplexes, e.g., [2,2′-thiobis(4-t-octylphenolate)]-n-butylamine nickel,[2,2′-thiobis(4-t-octylphenolate)]-2-ethylhexylamine nickel and[2,2′-thiobis(4-t-octylphenolate)]-triethanolamine nickel; and othernickel compounds, e.g., nickel bis(octylphenyl)sulfide and nickelisopropylxanthogenate. These light stabilizers may be used eitherindividually or in combination.

The component (S) is incorporated preferably at around 0.1 to 20 partsby weight per 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1)more preferably 1 to 10 parts by weight.

At a content of the component (S) below the above range, the curablecomposition of the present invention may have deterioratedweather-resistant adhesion to glass and other objects. The contentexceeding the above range is disadvantageous costwise. It is consideredthat the nickel-containing light stabilizer (S) brings about the effectof preventing light-caused deterioration of the adhesion-improvingeffect by the silane coupling agent used as the (T) component. Thenickel-containing light stabilizer (S) is considered to exhibit theabove effect to a higher extent than the other stabilizer.

Silane Coupling Agent (T)

The silane coupling agent as the (T) component for the present inventionimproves adhesion strength of the cured silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1) tothe base material and other objects. The agent is a compound which has agroup containing the silicon atom to which a hydrolyzable group isbonded (hereinafter referred to as hydrolyzable silicon group) and oneor more other functional groups. The concrete examples include thosedescribed earlier as the hydrolyzable groups, of which methoxy andethoxy are more preferable viewed from hydrolysis speed. The compoundpreferably has 2 or more hydrolyzable groups, still more preferably 3 ormore.

The functional groups useful for the present invention, other than thehydrolyzable silicon groups, include primary, secondary and tertiaryamino, mercapto, epoxy, carboxyl, vinyl, isocyanate, isocyanurate, andhalogen. Of these, primary, secondary or tertiary amino, epoxy,isocyanate and isocyanurate are more preferable, and isocyanate andepoxy are still more preferable.

The concrete examples of the silane coupling agents useful for thepresent invention include amino-containing silanes, e.g.,γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane,γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane,γ-(2-aminoethyl)aminopropyltrimethoxysilane,γ-(2-aminoethyl)aminopropylmethyldimethosysilane,γ-(2-aminoethyl)aminopropyltriethoxysilane,γ-(2-aminoethyl)aminopropylmethyldiethoxysilane,γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane,N-benzyl-γ-aminopropyltrimethoxysilane andN-vinylbenzyl-γ-aminopropyltriethoxysilane; mercapto-containing silanes,e.g., γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane,γ-mercaptopropylmethyldimethoxysilane andγ-mercaptopropylmethyldiethoxysilane; epoxy-containing silanes, e.g.,γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane,γ-glycidoxypropylmethyldimethoxysilane,β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane andβ-(3,4-epoxycyclohexyl)ethyltriethoxysilane; carboxysilanes, e.g.,β-carboxyethyltriethoxysilane,β-carboxyethylphenylbis(2-methoxyethoxy)silane andN-β-(carboxymethyl)aminoethyl-γ-aminopropyltrimethoxysilane; vinyl typeunsaturated group-containing silanes; e.g., vinyltrimethoxysilane,vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane andγ-acryloyloxypropylmethyltriethoxysilane; halogen-containing silanes,e.g., γ-chloropropyltrimethoxysilane; silane isocyanurates, e.g.,tris(trimethoxysilyl)isocyanurate; and isocyanate-containing silanes,e.g., γ-isocyanate propyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-isocyanate propylmethyldiethoxysilane andγ-isocyanate propylmethyldimethoxysilane. Moreover, the modifications ofthese compounds as their derivatives are also useful as the silanecoupling agents (T). These compounds include amino-modified silylpolymers, silylated amino polymers, unsaturated aminosilane complexes,block isocyanate silanes, phenylamino-long chain-alkyl silanes,aminosilylated silicone and silylated polyesters.

The silane coupling agent (T) is incorporated at 0.01 to 20 parts byweight per 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1),particularly preferably 0.1 to 10 parts by weight. These silane couplingagents (T) maybe used either individually or in combination.

The rubber composition (16) of the present invention may be incorporatedwith a tackifier, other than a silane coupling agent. The examples ofthe tackifiers, other than a silane coupling agent, include compoundshaving an epoxy or isocyanate group in the molecule, includingisocyanate polymers.

Other Components

The composition (16) of the present invention may be incorporated, asrequired, with one or more additives. The additives useful for thepresent invention include curing catalyst which promotes the silanolcondensation, storage stability improver which prevents curing of thecomposition (16) of the present invention while it is being stored,plasticizer, filler, aging inhibitor, ozone-caused aging inhibitor,phosphorus-based peroxide decomposer, lubricant and foaming agent.

Known curing catalysts may be used as the silanol condensing catalystfor the present invention. The concrete examples of these catalystsuseful for the present invention include titanate esters, e.g., those oftetrabutyl titanate and tetrapropyl titanate; tin carboxylates, e.g.,dibutyl tin dilaurate, dibutyl tin maleate, dibutyl tin diacetate, tinoctylate and tin naphthenate; product of the reaction between dibutyltin oxide and phthalate ester; dibutyl tin diacetylacetonate;organoaluminum compounds, e.g., aluminum trisacetylacetonate, aluminumtrisethylacetoacetate and diisopropoxy aluminum ethylacetoacetate;chelate compounds, e.g., zirconium tetraacetylacetonate and titaniumtetraacetylacetonate; lead octylate; amine-based compounds, and salts ofthese compounds and carboxylates, e.g., butylamine, octylamine,laurylamine, dibutylamine, monoethanolamine, diethanolamine,triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine,cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine,triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris(dimethylaminomethyl)phenol, morpholine, N-methyl morpholine,2-ethyl-4-methylimidazole and 1,8-diazabicyclo(5,4,0) undecene-7 (DBU);low-molecular-weight polyamide resins produced by the reactions betweenexcessive quantities of polyamines and polybasic acids; products of thereactions between excessive quantities of polyamines and epoxycompounds; silane coupling agents containing amino group, e.g.,γ-aminopropyl trimethoxy silane and N-(β-aminoethyl)aminopropylmethyldimethoxy silane; and other known catalysts, acidic or basic.These compounds may be used either individually or in combination.

The curing catalyst is incorporated at around 0.1 to 20 parts by weightper 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1),preferably around 1 to 10 parts by weight. The catalyst content belowthe above range may cause insufficient curing speed and insufficientextent of the curing reaction. The content beyond the above range isalso undesirable, because it may cause local heating or foamingoccurring during the curing process to make it difficult to produce thecured product of good properties, and also may deteriorate pot life toan unacceptable level and workability of the composition.

The storage stability improvers useful for the present invention includecompounds with silicon to which a hydrolyzable group is bonded, andesters of ortho-organic acids.

The concrete examples of the storage stability improvers includemethyltrimethoxy silane, methyltriethoxy silane, tetramethoxy silane,ethyltrimethoxy silane, dimethyldiethoxy silane,trimethylisobutoxysilane, trimethyl(n-butoxy)silane, n-butyltrimethoxysilane, and methyl orthoformate.

The plasticizers useful for the present invention includelow-molecular-weight ones, e.g., dioctylphthalate, high-molecular-weightones, and high-viscosity ones.

The concrete examples of these plasticizers include phthalate esters,e.g., those of dibutyl phthalate, diheptyl phthalate,di(2-ethylhexyl)phthalate, butyl benzyl phthalate and butyl phthalylbutyl glycolate; non-aromatic, dibasic acid esters, e.g., those ofdioctyl adipate and dioctyl cebacate; esters of polyalkylene glycol,e.g., those of diethylene glycol dibenzoate and triethylene glycoldibenzoate; phosphate esters, e.g., those of tricresyl phosphate andtributyl phosphate; paraffin chlorides; and hydrocarbon-based oils,e.g., alkyl diphenyl, polybutene, hydrogenated polybutene,ethylene/α-olefin oligomer, α-methyl styrene oligomer, biphenyl,triphenyl, triaryl dimethane, alkylene triphenyl, liquid polybutadiene,hydrogenated liquid polybutadiene, paraffin oil, naphthene oil, atacticpolypropylene and partially hydrogenated ter-phenyl. They may be usedeither individually or in combination. The plasticizer may beincorporated while the polymer is being produced.

Of these, hydrocarbon-based compounds free of unsaturated group, e.g.,hydrogenated polybutene, hydrogenated liquid polybutadiene, paraffinoil, naphthene oil and atactic polypropylene, are more preferable forvarious reasons, e.g., high compatibility with each component for thecomposition (16) of the present invention, limited effects on curingspeed of the rubber composition, good resistance to weather of the curedproduct, and cheapness.

The plasticizer may be used in place of the solvent during the processof introducing a reactive silicon group into the saturatedhydrocarbon-based polymer, for the purposes of, e.g., adjusting reactiontemperature and viscosity of the reaction system.

The plasticizer, when used, is incorporated preferably at 1 to 400 partsby weight per 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1),more preferably 1 to 150 parts, still more preferably 10 to 120 andparticularly preferably 20 to 100 parts by weight.

The concrete examples of the fillers include wood powder, pulp, cottonchips, asbestos, glass fibers, carbon fibers, mica, walnut shell powder,rice hull powder, graphite, diatomaceous earth, white clay, fumedsilica, settling silica, silicic anhydride, carbon black, calciumcarbonate, clay, kaolin, talc, titanium oxide, magnesium carbonate,quartz powder, glass beads, fine aluminum powder, flint powder, and zincpowder. Of these, more preferable ones are thixotropic fillers, e.g.,settling silica, fumed silica and carbon black; and calcium carbonate,titanium oxide and talc. They may be used either individually or incombination.

The aging inhibitors useful for the present invention include commonlyused known ones, e.g., sulfur-based ones, radical inhibitors andultraviolet ray absorbers.

The sulfur-based aging inhibitors useful for the present inventioninclude mercaptans, salts thereof, sulfides including sulfidecarboxylate esters and hindered phenol-based sulfides, polysulfides,dithiocarboxylates, thioureas, thiophosphates, sulfonium compounds,thioaldehydes, thioketones, mercaptals, mercaptols, monothio acids,polythio acids, thioamides, and sulfoxides.

The concrete examples of the sulfur-based aging inhibitors includemercaptans, e.g., 2-mercaptobenzothiazole; salts of mercaptans, e.g.,zinc salt of 2-mercaptobenzothiazole; sulfides, e.g.,4,4′-thio-bis(3-methyl-6-t-butyl phenol),4,4′-thio-bis(2-methyl-6-t-butyl phenol),2,2′-thio-bis(4-methyl-6-t-butyl phenol),bis(3-methyl-4-hydroxy-5-t-butylbenzyl)sulfide, terephthaloyldi(2,6-dimethyl-4-t-butyl-3-hydroxybenzyl)sulfide, phenothiazine,2,2′-thio-bis(4-octyl phenol)nickel, dilauryl thiodipropionate,distearyl thiodipropionate, dimyristyl thiodipropionate, ditridecylthiodipropionate, distearyl β,β′-thiodibutyrate, lauryl-stearylthiodipropionate and 2,2-thio[diethyl-bis-3-(3,5-di-t-butyl-4-hydroxyphenol)propionate]; polysulfides, e.g., 2-benzothiazole disulfide;dithiocarboxylates, e.g., zinc dibutyldithiocarbamate, zincdiethyldithiocarbamate, nickel dibutyldithiocarbamate, zincdi-n-butyldithiocarbamate, dibutyl ammonium dibutyldithiocarbamate, zincethyl-phenyl-dithiocarbamate and zinc dimethyldithiocarbamate;thioureas, e.g., 1-butyl-3-oxy-diethylene-2-thiourea,di-o-tolyl-thiourea and ethylene thiourea; and thiophosphates, e.g.,trilauryltrithiophosphate.

The above-described sulfur-based aging inhibitor preventsdecomposition/aging of the main chain under heating much moreefficiently than the other types for the composition (16) of the presentinvention, controlling the problems, e.g., residual surface tackiness.

The radical inhibitors useful for the present invention includephenol-based ones, e.g., 2,2-methylene-bis(4-methyl-6-t-butyl phenol)and tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane; and amine-based ones, e.g., phenyl-β-naphthylamine,α-naphthylamine, N,N′-sec-butyl-p-phenylenediamine, phenothiazine andN,N′-diphenyl-p-phenylenediamine.

The ultraviolet ray absorbers useful for the present invention include2-(2′-hydroxy-3′,5′-di-t-butylphenyl)benzotriazole andbis(2,2,6,6-tetramethyl-4-piperidine)cebacate.

Curable Composition (16) and its Uses

The curable composition (16) of the present invention contains thecurable composition with the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber as thecomponent (A1), as described in detail earlier. More concretely, itcontains

-   (a) the organic polymer (Z) containing the hydrolyzable silyl group    represented by the general formula [III] and essentially no    unsaturated double bond in the main chain,-   (b) a nickel-containing light stabilizer (S), and-   (c) a silane coupling agent (T).    It can be suitably used for electric/electronic device members,    transportation machines, and civil engineering/construction, medical    and leisure areas, as described earlier.

The curable composition (16) of the present invention can be used assealants, potting agents, coating materials or adhesives forelectric/electronic device members, transportation machines, and civilengineering/construction, and leisure areas.

In other words, the present invention provides sealants, potting agents,coating materials and adhesives, composed of the curable compositioncontaining the (a) organic polymer (Z), (b) nickel-containing lightstabilizer (S) and (C) silane coupling agent (T).

Curable Rubber Composition (17)

The curable rubber composition (17) of the present invention containsthe silyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1), and a sulfur-based aging inhibitor (U).

A silanol condensing catalyst is used, as required, to cure the (A1)component as the major ingredient of the curable rubber composition (17)of the present invention.

The concrete examples of the condensing catalysts useful for the presentinvention include titanate esters, e.g., those of tetrabutyl titanateand tetrapropyl titanate; tin carboxylates, e.g., dibutyl tin dilaurate,dibutyl tin maleate, dibutyl tin diacetate, tin octylate and tinnaphthenate; product of the reaction between dibutyl tin oxide andphthalate ester; dibutyl tin diacetylacetonate; organoaluminumcompounds, e.g., aluminum trisacetylacetonate, aluminumtrisethylacetoacetate and diisopropoxy aluminum ethylacetoacetate;chelate compounds, e.g., zirconium tetraacetylacetonate and titaniumtetraacetylacetonate; lead octylate; amine-based compounds, and salts ofthese compounds and carboxylates, e.g., butylamine, monoethanolamine,triethylenetetramine, guanidine, 2-ethyl-4-methylimidazole and1,3-diazabicyclo(5,4,6)endecene-7 (DBU); and other known silanolcondensing catalysts, acidic or basic.

Sulfur-based Aging Inhibitor (U)

The sulfur-based aging inhibitors useful for the present invention asthe (U) component include mercaptans, salts thereof, sulfides includingsulfide carboxylate esters and hindered phenol-based sulfides,polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfoniumcompounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothioacids, polythio acids, thioamides, and sulfoxides.

The concrete examples of the sulfur-based aging inhibitors as the (U)component include

mercaptans, e.g., 2-mercaptobenzothiazole;

salts of mercaptans, e.g., zinc salt of 2-mercaptobenzothiazole;

sulfides, e.g., 4,4′-thio-bis (3-methyl-6-t-butyl phenol),4,4′-thio-bis(2-methyl-6-t-butyl phenol),2,2′-thio-bis(4-methyl-6-t-butyl phenol),bis(3-methyl-4-hydroxy-5-t-butylbenzyl)sulfide, terephthaloyldi(2,6-dimethyl-4-t-butyl-3-hydroxybenzyl)sulfide, phenothiazine,2,2′-thio-bis(4-octyl phenol)nickel, dilauryl thiodipropionate,distearyl thiodipropionate, dimyristyl thiodipropionate, ditridecylthiodipropionate, distearyl β,β′-thiodibutyrate, lauryl-stearylthiodipropionate and 2,2-thio[diethyl-bis-3-(3,5-di-t-butyl-4-hydroxyphenol)propionate];

polysulfides, e.g., 2-benzothiazole disulfide;

dithiocarboxylates, e.g., zinc dibutyldithiocarbamate, zincdiethyldithiocarbamate, nickel dibutyldithiocarbamate, zincdi-n-butyldithiocarbamate, dibutyl ammonium dibutyldithiocarbamate, zincethyl-phenyl-dithiocarbamate and zinc dimethyldithiocarbamate;

thioureas, e.g., 1-butyl-3-oxy-diethylene-2-thiourea,di-o-tolyl-thiourea and ethylene thiourea; and

thiophosphates, e.g., trilauryltrithiophosphate. Other compounds may beused for the present invention, so long as they are sulfur-based oneshaving an aging inhibiting function.

The above-described sulfur-based aging inhibitor (U) preventsdecomposition/aging of the main chain under heating much moreefficiently than the other types for the composition (17) of the presentinvention, controlling the problems, e.g., residual surface tackiness.

The above-described sulfur-based aging inhibitor (U) is incorporatednormally at 0.01 to 10 parts by weight per 100 parts by weight of thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1), preferably 0.1 to 5 parts by weight. It shows asufficient effect of improving resistance of the composition to heatwithout causing any problem, e.g., coloration.

One or more commonly used aging inhibitors may be used in combination ofthe sulfur-based aging inhibitor (U). These aging inhibitors includephenol-based radical inhibitor, e.g.,2,2′-methylene-bis(4-methyl-6-t-butyl phenol) and tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propio nate] methane;ultraviolet ray absorber, e.g.,2-(2′-hydroxy-3′,5′-di-t-butylphenyl)benzotriazole andbis(2,2,6,6-tetramethyl-4-piperidine)cebacate; metal deactivator,ozone-caused aging inhibitor, light stabilizer, amine-based radicalchaining inhibitor, phosphorus-based peroxide decomposer; citric acid;and phosphoric acid.

Moreover, various silane compounds may be used as the property adjusterfor the present invention, to control strength, elongation and otherproperties of the cured product over a wide range. The concrete examplesof these compounds include the following silicon compounds having one ormore silanol group or other hydrolyzable groups, although not limitedthereto: (CH₃)₃SiOH, (CH₃CH₂)₃SiOH, (CH₃CH₂CH₂)₃SiOH, (C₆H₅—)₃SiOH,(C₆H₅—)₂(CH₃—)SiOH, (CH₃—)₂(C₆H₅—)SiOH,

(CH₃)₂Si (OCH₃)₂, (CH₃CH₂)₂Si(OCH₃)₂, (CH₃)₂Si(OCH₂CH₃)₂,(CH₃CH₂)₂Si(OCH₂CH₃)₂, (C₆H₅)₂Si(OCH₂CH₃)₂, (C₆H₅)₂Si(OCH₃)₂,(C₆H₅)₂Si(OH)₂, (CH₃—C₆H₅)₂Si(OCH₃)₂, (CH₃—C₆H₅)₂Si(OH)₂,(CH₃)₂Si(OCH₂CH₂OCH₃)₂, (CH₃CH₂)₂Si(OCH₂CH₂OCH₃)₂,(CH₃)(CH₃CH₂)Si(OCH₃)₂, (C₆H₅)(CH₃)Si(OH)₂, (C₆H₅)(CH₃CH₂)Si(OH)₂,(C₆H₅) (CH₃)Si(OCH₃)₂, (C₆H₅)(CH₃CH₂)Si(OH)₂,

(CH₃)₃Si—NH—Si(CH₃)₃, (CH₃)₃Si—N(CH₃)₂, (CH₃)₃Si—NH—CO—NH—Si(CH₃)₃,

In the above formulae, R is hydrogen atom, or a hydrocarbon group of 1to 20 carbon atoms.

The methods for incorporating the silicon compound fall into 3 generalcategories.

The first method merely adds the silicon compound to thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1), wherein it is uniformly dispersed and dissolvedby carefully setting the conditions, e.g., temperature and stirringconditions, as required in consideration of the silicon compoundproperties. In this case, the composition may not be necessarilytransparent completely, and can adequately achieve the objectives evenwhen it is not transparent, so long as the composition is sufficientlydispersed therein. A dispersibility improver, e.g., surfactant, may beused, as required.

The second method mixes a given quantity of the silicon compound withthe final product, when it is used. For example, when the composition isused as a two-liquid type sealant, the silicon compound may be mixed asthe third component with the base and the curing agent for thecomposition.

The third method reacts the silicon compound beforehand with thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1) in the presence of a silanol condensing catalyst,as required. When the silicon compound is reacted with moisture into acompound having a silanol group in the molecule, a required quantity ofwater is added to the reaction system, and afterwards evaporated offunder a vacuum and heating, to achieved the object.

The curable rubber composition (17) of the present invention, comprisingthe silyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1) and a sulfur-based aging inhibitor (U) as themajor ingredients, may be incorporated, as required, with one or moreadditives, to begin with the various silane compounds described above asthe property adjusters. The other additives useful for the presentinvention include various types of filler, plasticizer, silanolcondensing catalyst which promotes curing of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1),aging inhibitor other than the sulfur-based aging inhibitor (U)ultraviolet ray absorber, lubricant, pigment, foaming agent, tackifier,and water.

The concrete examples of the fillers include wood powder, pulp, cottonchips, asbestos, glass fibers, carbon fibers, mica, walnut shell powder,rice hull powder, graphite, diatomaceous earth, white clay, fumedsilica, settling silica, silicic anhydride, carbon black, calciumcarbonate, clay, talc, titanium oxide, magnesium carbonate, quartz, finealuminum powder, flint powder, and zinc powder.

They may be used either individually or in combination.

The concrete examples of these plasticizers include:

hydrocarbon-based compounds, e.g., polybutene, hydrogenated polybutene,ethylene/α-olefin cooligomer, α-methyl styrene oligomer, biphenyl,triphenyl, triaryl dimethane, alkylene triphenyl, liquid polybutadiene,hydrogenated liquid polybutadiene, alkyl diphenyl, process oil, paraffinoil, naphthene oil and partially hydrogenated ter-phenyl;

paraffin chlorides;

phthalate esters, e.g., those of dibutyl phthalate, diheptyl phthalate,di(2-ethylhexyl)phthalate, butyl benzyl phthalate and butyl phthalylbutyl glycolate;

non-aromatic, dibasic acid esters, e.g., those of dioctyl adipate anddioctyl cebacate;

esters of polyalkylene glycol, e.g., those of diethylene glycol benzoateand triethylene glycol dibenzoate; and

phosphate esters, e.g., those of tricresyl phosphate and tributylphosphate. Of these, saturated hydrocarbon-based compounds areparticularly more preferable. They may be used either individually or incombination. The plasticizer may be used in place of the solvent duringthe process of introducing a hydrolyzable silyl group into theethylene/α-olefin/non-conjugated polyene random copolymer rubber (A₀),for the purposes of, e.g., adjusting reaction temperature and viscosityof the reaction system.

Moreover, the curable rubber composition (17) of the present inventionmay be incorporated with various tackifiers to further improve itsadhesion.

The concrete examples of the tackifiers useful for the present inventioninclude silane coupling agents, e.g., epoxy resin, phenolic resin,aminosilane and epoxysilane compounds; alkyl titanates; and aromaticpolyisocyanates. These may be used either individually or incombination, to improve adhesion of the composition to various types ofobjects.

The curable rubber composition (17) of the present invention can besuitably used for various materials, e.g., adhesives, tackifiers,paints, sealant compositions, waterproof materials, spray materials,shaping materials and casting rubber materials.

Curable Rubber Composition (17) and its Uses

The curable rubber composition (17) of the present invention containsthe curable composition with the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber as thecomponent (A1), as described earlier. More concretely, it contains theorganic polymer (Z) and a sulfur-based aging inhibitor (U). It can besuitably used for electric/electronic device members, transportationmachines, and civil engineering/construction, medical and leisure areas,as described earlier.

The curable rubber composition (17) of the present invention can be usedas sealants, potting agents, coating materials or adhesives forelectric/electronic device members, transportation machines, and civilengineering/construction, and leisure areas.

Curable Composition (18)

The curable composition (18) of the present invention contains thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1), and a compound having, in the molecule, anunsaturated group capable of triggering polymerization by reacting withoxygen in air and/or a photopolymerizable material (V).

The curable composition (18) of the present invention contains thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1) preferably at 10% or more, more preferably at 20%or more, still more preferably at 30% or more.

The curable composition (18) of the present invention exhibits excellentcharacteristics with respect to curing speed and resistance to weather,which is mainly derived from the ethylene/α-olefin/non-conjugatedpolyene random copolymer rubber (A1) containing the hydrolyzable silylgroup.

Oxidative-polymerizable Material and/or Photopolymerizavle Material (V)

The curable composition (18) of the present invention is incorporatedwith the (V) component of a compound having, in the molecule, anunsaturated group capable of triggering polymerization by reacting withoxygen in air and/or a photopolymerizable material, in order to enhanceits weather-resistant adhesion. They can exhibit their functions whenused individually, and may be used in combination.

Of the above-described materials for the (V) component, the compoundhaving, in the molecule, an unsaturated group capable of triggeringpolymerization by reacting with oxygen in air means, in short, anoxidative-polymerizable material.

The concrete examples of the oxidative-polymerizable materials includeester compounds of unsaturated higher fatty acids and alcohols;diene-based polymers and copolymers, e.g., those of 1,2-polybutadienes,1,4-polybutadienes and dienes of 5 to 8 carbon atoms; and variousmodifications of these polymers and copolymers, e.g., those modifiedwith maleic acid or boiled oil. Reactivity of oxidative polymerizationdepends on, e.g., reaction temperature, humidity, and presence orabsence of light and additive.

It is therefore considered that, when a compound having, in themolecule, an unsaturated group capable of triggering polymerization byreacting with oxygen in air is added as the (V) component, it works asthe weather-resistant adhesion improver more strongly when irradiatedwith light, owing to its ability of forming a still harder coating filmon the adhesion surface with an object, e.g., glass. However, it showsno deterioration of the initial adhesion strength.

When an ester compound with an ester of an unsaturated higher fatty acidand alcohol as the major ingredient is incorporated as the (V)component, the curable composition (18) will have markedly improvedweather-resistant adhesion to various types of glass, e.g., heat rayreflective glass. The unsaturated higher fatty acid component for theester of an unsaturated higher fatty acid and alcohol preferably has atleast 10 carbon atoms in the molecule, and may have each at least oneunsaturated group and carboxyl group.

The concrete examples of the ester compounds of unsaturated higher fattyacids include those produced by the condensation of unsaturated higherfatty acids, e.g., oleic, linolic, linolenic, eleostearic, licanic,ricinolic or arachidonic acid, with alcohol selected from the groupconsisting of monovalent alcohols (e.g., methanol and ethanol), divalentalcohols (e.g., ethylene glycol and propylene glycol), trivalentalcohols (e.g., trimethylol propane and glycerin), tetravalent alcohols(e.g., pentaerythritol), hexavalent alcohols (e.g., sorbit), andorganosilicon compounds with hydroxyl group bonded via an organic groupbonded to silicon atom.

It is known that a saturated fatty acid group has much lower reactivityfor the oxidative polymerization than an unsaturated fatty acid group,and that unsaturated fatty acid groups increase reactivity in proportionto number of the double bonds they contain and degree of conjugate.Therefore, of the ester compounds of unsaturated higher fatty acids, theones having an iodine value of 100 or more are more preferable for theirhigh reactivity.

The ester compounds of unsaturated higher fatty acids and having aniodine value of 100 or more may be produced by condensation of anunsaturated higher fatty acid and alcohol, as described above. However,use of a drying oil is more practical costwise, because it is readilyavailable. These drying oils include those comprising, as the majoringredient, a triglycerin ester, i.e., ester of an unsaturated higherfatty acid and glycerin, e.g., flaxseed oil, china wood oil, soybeanoil, hemp-seed oil, isano oil, urushi kernel oil, Perilla oil, oiticicaoil, kaya oil, walnut oil, poppy oil, cherry seed oil, pomegranate seedoil, safflower oil, tobacco seed oil, touhaze kernel oil, rubber seedoil, sunflower seed oil, grape kernel oil, balsam seed oil and honewortseed oil.

These drying oils may contain ester compounds of unsaturated higherfatty acids having 10 or more carbon atoms, ester compounds ofunsaturated higher fatty acids having less than 10 carbon atoms,alcohols, unsaturated fatty acids, and saturated fatty acids. Estercompounds of unsaturated higher fatty acids having 10 or more carbonatoms preferably account for at least 80% by weight, most preferably100% by weight of the drying oil.

As described earlier, reactivity for the oxidative polymerizationincreases in proportion to degree of conjugate of the unsaturated fattyacid group. Therefore, drying oils with a triglycerin ester ofconjugate-based unsaturated higher fatty acids, e.g., eleostearic,licanic, punicic or canulupinic acid, as the major ingredient have highreactivity for the oxidative polymerization to improve weather-resistantadhesion of the composition more efficiently, and hence most desirable.The concrete examples of those drying oils with a triglycerin ester ofconjugate-based unsaturated higher fatty acids as the major ingredientinclude china wood, oiticica, pomegranate seed and balsam seed oils.

These compounds with an unsaturated group in the molecule capable oftriggering the polymerization by reacting with oxygen in air may be usedeither individually or in combination.

Of the above-described materials for the (V) component, thephotopolymerizable material means, in short, a compound having anunsaturated group whose double bond is activated when irradiated withlight to trigger the polymerization. Various materials are known to fallinto this category, including organic monomers, oligomers, resins andcompositions containing one or more of them. Any relevant commercialmaterial may be used for the present invention. The photopolymerizablematerial, when used as the (V) component, works as the weather-resistantadhesion improver, because it can form a hard coating film on theadhesion surface with an object, e.g., glass, when irradiated withlight. However, it shows no deterioration of the initial adhesionstrength.

The photopolymerizable unsaturated groups contained in thephotosensitive resins for the photopolymerization systems can berepresented by vinyl, allyl, vinyl ether, vinyl thioether, vinyl amino,acetylenic unsaturated, acryloyl, methacryloyl, styryl and cinnamoylgroup. Of these, acryloyl and methacryloyl are more preferable, becauseof their high polymerization initiation efficiency.

The examples of the photosensitive resins containing acryloyl ormethacryloyl group for the photopolymerization systems includeacrylamide derivatives, methacrylamide derivatives and (meth)acrylates,of which (meth)acrylates are more preferable, because of theiravailability for various types.

(Meth)acrylates in this specification is a generic term including bothacrylates and methacrylates.

When a mono-functional photopolymerizable material with a (meth)acrylateas the major ingredient has one photosensitive group (unsaturatedgroup), only a linear polymer is formed by the photopolymerization. In amulti-functional (meth)acrylate having two or more photosensitive(unsaturated) groups, on the other hand, photopolymerization andphotocrosslinking take place simultaneously, to form polymer moleculesof network structures. Therefore, such a (meth)acrylate is morepreferable, because a harder coating film can be formed on the adhesioninterface, to enhance the effect of improving weather-resistantadhesion.

The concrete examples of the multi-functional (meth)acrylates includepropylene, butylene or ethylene glycol di(meth)acrylates having 2functional groups; trimethylolpropane tri(meth)acrylate andpentaerythritol tri(meth)acrylate having 3 functional groups; andpentaerythritol tetra(meth)acrylate, dipentaerythritolpenta(meth)acrylate and dipentaerythritol hexa(meth)acrylate having 4 ormore functional groups. Moreover, the examples of the oligomers includeoligoesters having a molecular weight of 10,000 or less, e.g.,polyethylene glycol di(meth)acrylate and polypropylene glycoldi(meth)acrylate. The multi-functional (meth)acrylates preferably have 2or more acrylic- or methacrylic-based unsaturated groups, morepreferably 3 or more. The unsaturated acrylic-based compound has thehigher effect of improving weather-resistant adhesion as its number offunctional groups increases.

The other examples of the photopolymerizable materials include polyvinylcinnamates and azide resins.

The polyvinyl cinnamates include cinnamate ester compounds of polyvinylalcohol, known as photosensitive resins with cinnamoyl group as thephotosensitive group, and many other vinyl polycinnamate derivatives.

The azide resins include rubber photosensitive liquids, known asphotosensitive resins with azide group as the photosensitive group andnormally incorporated with a diazide compound for the photosensitivegroup, and others described in detail in “Photosensitive Resins,published on Mar. 17, 1972 by the Society of Printing, pp.93, 106 and117). These may be used either individually or in combination, andincorporated, as required, with a photosensitizer.

These photopolymerizable materials may be used either individually or incombination. When the (V) component is required to exhibit its effect ofimproving weather-resistant adhesion more securely and more quickly,incorporation of a photosensitizer is effective for the above purpose.When the (V) component, which is a compound having, in the molecule, anunsaturated group capable of triggering polymerization by reacting withoxygen in air and/or a photopolymerizable material, is incorporated inthe composition (18) of the present invention, the curable compositioncontaining the saturated hydrocarbon-based polymer having a reactivesilicon group can be greatly improved in its weather-resistant adhesion.On top of that, the (V) component has no adverse effect on theproperties of the cured compositions. It is incorporated preferably at0.1 to 20 parts by weight per 100 parts by weight of the (A1) component,particularly preferably 1 to 10 parts by weight. At below 0.1 part byweight, it may not sufficiently exhibit the effect of improvingweather-resistant adhesion. At above 20 parts, it may deterioratestorage stability of the sealant composition.

The curable composition (18) of the present invention, containing the(A1) and (V) components, shows better adhesion and weather-resistantadhesion to a base material than a curable composition free of the (V)component, because the (V) component is cured by the actions of oxygenand/or light. These characteristics are exhibited even when thecomposition contains no silane coupling agent, described later. However,it will exhibit still better adhesion and weather-resistant adhesion,when incorporated with a silane coupling agent.

The curable composition (18) of the present invention may beincorporated, as required, with one or more additives. The additivesuseful for the present invention include silane coupling agent, curingcatalyst which promotes the silanol condensation, property adjusterwhich adjusts the tensile-related properties of the cured product,plasticizer, filler, adhesion improver, aging inhibitor, radicalinhibitor, ultraviolet ray absorber, metal deactivator, ozone-causedaging inhibitor, light stabilizer, phosphorus-based peroxide decomposer,lubricant, pigment, and foaming agent.

The silane coupling agent, which is incorporated as required in thecurable composition (18) of the present invention, improves adhesionstrength of the cured silyl-containing ethylene/α-olefin/non-conjugatedpolyene random copolymer rubber (A1) to the base material and otherobjects. It is a compound which has a group containing the silicon atomto which a hydrolyzable group is bonded (hereinafter referred to ashydrolyzable silicon group) and one or more other functional groups.

The concrete examples include those described earlier as thehydrolyzable groups, of which methoxy and ethoxy are more preferableviewed from hydrolysis speed. It preferably has 2 or more hydrolyzablegroups, still more preferably 3 or more.

The functional groups useful for the present invention, other than thehydrolyzable silicon groups, include primary, secondary and tertiaryamino, mercapto, epoxy, carboxyl, vinyl, isocyanate, isocyanurate, andhalogen. Of these, primary, secondary or tertiary amino, epoxy,isocyanate and isocyanurate are more preferable, and isocyanate andepoxy are still more preferable.

The concrete examples of the silane coupling agents useful for thepresent invention include amino-containing silanes, e.g.,γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane,γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane,γ-(2-aminoethyl)aminopropyltrimethoxysilane,γ-(2-aminoethyl)aminopropylmethyldimethoxysilane,γ-(2-aminoethyl)aminopropyltriethoxysilane,γ-(2-aminoethyl)aminopropylmethyldiethoxysilane,γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxylsilane,N-benzyl-γ-aminopropyltrimethoxylsilane andN-vinylbenzyl-γ-aminopropyltriethoxylsilane; mercapto-containingsilanes, e.g., γ-mercaptopropyltrimethoxysilane,γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilaneand γ-mercaptopropylmethyldiethoxysilane; epoxy-containing silanes,e.g., γ-glycidoxypropyltrimethoxysilane,γ-glycidoxypropyltriethoxysilane,γ-glycidoxypropylmethyldimethoxysilane,γ-(3,4-epoxycyclohexyl)ethyltrimethoxysilane andγ-(3,4-epoxycyclohexyl)ethyltriethoxysilane; carboxysilanes, e.g.,γ-carboxyethyltriethoxysilane,γ-carboxyethylphenylbis(2-methoxyethoxy)silane andN-β-(carboxymethyl)aminoethyl-γ-aminopropyltrimethoxysilane; vinyl typeunsaturated group-containing silanes; e.g., vinyltrimethoxysilane,vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane andγ-acryloyloxypropylmethyltriethoxysilane; halogen-containing silanes,e.g., γ-chloropropyltrimethoxysilane; silane isocyanurates, e.g.,tris(trimethoxysilyl)isocyanurate; and isocyanate-containing silanes,e.g., γ-isocyanate propyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-isocyanate propylmethyldiethoxysilane andγ-isocyanate propylmethyldimethoxysilane. Moreover, the modifications ofthese compounds as their derivatives are also useful as the silanecoupling agents. These compounds include amino-modified silyl polymers,silylated amino polymers, unsaturated aminosilane complexes, blockisocyanate silanes, phenylamino-long chain-alkyl silanes, aminosilylatedsilicone and silylated polyesters.

The silane coupling agent, which is optionally used for the presentinvention, is incorporated preferably at 0.1 to 20 parts by weight per100 parts by weight of the ethylene/α-olefin/non-conjugated polyenerandom copolymer rubber (A1) containing hydrolyzable silyl group,particularly preferably 0.5 to 10 parts by weight. These silane couplingagents may be used either individually or in combination. Thecomposition (18) of the present invention may be further incorporatedwith a tackifier other than the silane coupling agent.

The plasticizer may be used in place of the solvent during the processof introducing a hydrolyzable silyl group into theethylene/α-olefin/non-conjugated polyene random copolymer rubber (A₀),for the purposes of, e.g., adjusting reaction temperature and viscosityof the reaction system.

The concrete examples of these additives are described in, e.g.,Japanese Patent Publication Nos. 69659/1992 and 108928/1995, andJapanese Patent Laid-Open Publication Nos. 254149/1988 and 22904/1989.

The curable composition (18) of the present invention shows a notableeffect of improving adhesion to a variety of objects, e.g., inorganicbases of glass, aluminum, stainless steel, zinc, copper and mortar, andorganic bases of vinyl chloride, acrylic resin, polyester, polyethylene,polypropylene and polycarbonate, in the presence or absence of a primer,more significantly in the absence of a primer.

The curable composition (18) of the present invention shows a notableeffect of improving weather-resistant adhesion to various types ofglass, e.g., common inorganic glass (float glass), particularlynoticeably when used as a sealant composition for heat ray reflectiveglass. The heat ray reflective glass to which the curable composition(18) of the present invention is applicable means optically functionalglass coated, on the surface, with a film of, e.g., metal, metal nitrideor metal oxide, to reflect or absorb light of specific wavelength.

The effect of the unsaturated compound capable of reacting with oxygenin air is also observed, even when various additives are incorporated.

More concretely, the curable composition (18) of the present invention,when used as an elastomer sealant for construction works, or a sealantfor laminated glass or rust-prevention or water-proof of edges (cutsections) of wired or laminated glass, will have still improved adhesionand weather-resistant adhesion of the sealant to various objects, whenincorporated with the above compounds.

Curable Composition (18) and its Uses

The curable composition (18) of the present invention contains thecurable composition with the hydrolyzable silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber as thecomponent (A1), as described earlier. More concretely, it contains theorganic polymer (Z) and a compound having, in the molecule, anunsaturated group capable of triggering polymerization by reacting withoxygen in air and/or photopolymerizable material (V). It can be suitablyused for electric/electronic device members, transportation machines,and civil engineering/construction, medical and leisure areas, asdescribed earlier.

The curable composition (18) is preferably incorporated further with theabove-described silane coupling agent.

The curable rubber composition (18) of the present invention can be usedas sealants, potting agents, coating materials or adhesives forelectric/electronic device members, transportation machines, and civilengineering/construction, and leisure areas.

In other words, the present invention provides sealants, potting agents,coating materials and adhesives, composed of the curable compositioncontaining the organic polymer (Z) and a compound having, in themolecule, an unsaturated group capable of triggering polymerization byreacting with oxygen in air and/or photopolymerizable material (V).

The curable composition is preferably incorporated further with theabove-described silane coupling agent, when it is used for sealants,potting agents, coating materials and adhesives.

Tackifier Composition (19)

The tackifier composition (19) of the present invention contains thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1), a tackiness imparting resin (W) and a curingcatalyst (H) composed of a specific organozirconium compound (H1) or aspecific organoaluminum compound (H2).

Tackiness Imparting Resin (W)

A tackiness imparting resin (W) can be used for the present invention,to adjust the tackiness characteristics of the composition.

The tackiness imparting resin (W) is not limited. These resins usefulfor the present invention include those having an acidic group, e.g.,rosin ester resin, phenol resin, xylene resin, xylene/phenol resin andterpene/phenol resin; various petroleum-based resins, e.g., aromatic-,aliphatic/aromatic copolymer- and alicyclic-based resins of relativelylow polarity; and common tackiness imparting resins, e.g., coumaroneresin, low-molecular-weight polyethyrene resin and terpene resin.

The concrete examples of these resins include, although not limited to,those of relatively low polarity, e.g., Petrosin 801™ (Mitui Chemicals),Neopolymer S™ (NIPPON PETROCHEMICALS), Tackiace A100™ (Mitui Chemicals),Quintone 1500™ (ZEON CORP.), FTR6100™ (Mitui Chemicals), Vicolastic A75™(Hercules), Coumarone C-90™ (Nippon Steel Chemical Group); and thosehaving a relatively low polar group, e.g., YS Polystar T-115™ and YSPolystar S-145™ (Yasuhara Yushi), Steperite Ester 7™ (Hercules), andNeopolymer E-100™ (NIPPON PETROCHEMICALS).

Content of the tackiness imparting resin (W) varies depending on itstype used. However, it is incorporated preferably at up to 140 parts byweight per 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1).At above 140 parts, it may not give the composition of good tackinesscharacteristics.

Curing Catalyst (H)

The curing catalyst (H) for the present invention is an organozirconiumcompound (H1) represented by the following general formula [VIII] or anorganoaluminum compound (H2) represented by the following general formul[IX]. Use of the curing catalyst (H) greatly improves releasability ofthe tackifier composition (19) of the present invention from siliconereleasing paper.

wherein, “n” is an integer of 0 to 4, R is a monovalent hydrocarbongroup of 1 to 20 carbon atoms, and Y is a group selected from the groupconsisting of hydrocarbon of 1 to 8 carbon atoms, halogenatedhydrocarbon, cyanoalkyl, alkoxyl, halogenated alkoxyl, cyanoalkoxy andamino group, which may be the same or different, and

wherein, “p” is an integer of 0 to 3, R is a monovalent hydrocarbongroup of 1 to 20 carbon atoms, and Y is a group selected from the groupconsisting of hydrocarbon of 1 to 8 carbon atoms, halogenatedhydrocarbon, cyanoalkyl, alkoxyl, halogenated alkoxyl, cyanoalkoxy andamino group, which may be the same or different.

The organozirconium compound (H1) or the organoaluminum compound (H2)means alkoxide-based compound or cheleate compound of zirconium oraluminum, represented by the above general formula [VIII] or [IX],wherein an organic group is bonded to zirconium or aluminum. It may be amonomer or an associated compound.

The concrete examples of these compounds include, but not limited to,alkoxide-based compounds, e.g., (C₂H₅O)₄Zr, (iso-C₃H₇O)₄Zr,(n-C₄H₉O)₄Zr, (C₈H₁₇O)₄Zr, (iso-C₃H₇O)₃Al, (iso-C₃H₇O)₂Al (sec-C₄H₉O)and (sec-C₄H₉O)₃Al; and cheleate compounds, e.g.,

Zr(acac)₄ (zirconium tetraacetylacetonate, and so forth), (n-C₄H₉O)₃Zr(acac), (n-C₄H₉O)₂Zr (acac)₂, (n-C₄H₉O)Zr (acac)₃, (iso-C₃H₇O)₂Al(acac), Al(acac)₃, (iso-C₃H₇O)₂Al (ethyl acetoacetate) and Al (ethylacetoacetate)₃.

The organozirconium compound (H1) or organoaluminum compound (H2) may beuseful, even when it is associated into a trimer or tetramer. Thesecuring catalysts (H) may be used either individually or in combination.

The curing catalyst (H) is incorporated preferably at 0.01 to 20 partsby weight per 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1).At below 0.01 part, the curing catalyst (H) may not sufficiently exhibitits catalytic effect. At above 20 parts, on the other hand, it willexcessively promote the curing reaction, which will deteriorateworkability of applying the tackifier composition to a base.

The curing catalyst (H) for the present invention is on a level incuring activity with the organotin-base compound, which has been widelyused as the curing catalyst, causes no coloration of the tackifier,unlike an alkyl titanate-based compound used as the catalyst, and isexcellent in productivity and external appearances.

Other Components

The-tackifier composition (19) of the present invention may beincorporated, as required, with one or more additives within limits notdetrimental to the object of the present invention. The additives usefulfor the present invention include adhesion improver, property adjuster,storage stability improver, plasticizer or softening agent, filler,aging inhibitor, ultraviolet ray absorber, metal deactivator,ozone-caused aging inhibitor, light stabilizer, amine-based radicalchaining inhibitor, phosphorus-based peroxide decomposer, antioxidant,lubricant, pigment, foaming agent and surfactant.

The adhesion improvers useful for the present invention include commonlyused adhesives, silane coupling agents, e.g., aminosilane and epoxysilane compounds; and others. The concrete examples of these adhesionimprovers include phenolic resin, epoxy resin, γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)aminopropyl methyldimethoxysilane,coumarone/indene resin, rosin ester resin, terpene/phenol resin,α-methyl styrene/vinyl toluene copolymer, polyethylmethyl styrene, alkyltitanate, and aromatic polyisocyanate. The adhesion improver, when used,is incorporated preferably at about 1 to 50 parts by weight per 100parts by weight of the silyl-containing ethylene/α-olefin/non-conjugatedpolyene random copolymer rubber (A1), more preferably 5 to 30 parts byweight.

The storage stability improvers useful for the present invention includeesters of ortho-organic acids.

The storage stability improver, when used, is incorporated preferably atabout 0.5 to 20 parts by weight per 100 parts by weight of thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1), more preferably 1 to 10 parts by weight.

The plasticizer useful for the present invention is also not limited,and any commonly used one may be used. Preferably, it should becompatible with each component for the rubber composition of the presentinvention.

The concrete examples of these plasticizers include:

hydrocarbon-based compounds, e.g., polybutene, hydrogenated polybutene,ethylene/α-olefin cooligomer, α-methyl styrene oligomer, biphenyl,triphenyl, triaryl dimethane, alkylene triphenyl, liquid polybutadiene,hydrogenated liquid polybutadiene, alkyl diphenyl, partiallyhydrogenated ter-phenyl, paraffin oil, naphthene oil and atacticpolypropylene;

paraffin chlorides;

phthalate esters, e.g., those of dibutyl phthalate, diheptyl phthalate,di(2-ethylhexyl)phthalate, butyl benzyl phthalate, dioctyl phthalate andbutyl phthalyl butyl glycolate;

non-aromatic, dibasic acid esters, e.g., those of dioctyl adipate anddioctyl cebacate;

esters of polyalkylene glycol, e.g., those of diethylene glycol benzoateand triethylene glycol dibenzoate;

phosphate esters, e.g., those of tricresyl phosphate and tributylphosphate; and

polypropylene glycol. Of these, saturated hydrocarbon-based compoundsare more preferable. They may be used either individually or incombination.

Of the above-described compounds, hydrocarbon-based compounds free ofunsaturated group, e.g., hydrogenated polybutene, hydrogenated liquidpolybutadiene, paraffin oil, naphthene oil and atactic polypropylene,are more preferable for various reasons, e.g., high compatibility witheach component for the rubber composition of the present invention,limited effects on curing speed of the rubber composition, goodresistance to weather of the cured product, and cheapness.

The plasticizer may be used in place of the solvent during the processof introducing a hydrolyzable silyl group into the above-describedethylene/α-olefin/non-conjugated polyene random copolymer rubber (A₀),for the purposes of, e.g., adjusting reaction temperature and viscosityof the reaction system.

The plasticizer, when used, is incorporated preferably at about 10 to500 parts by weight per 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1),more preferably about 20 to 300 parts by weight.

The concrete examples of the fillers include wood powder, pulp, cottonchips, asbestos, glass fibers, carbon fibers, mica, walnut shell powder,graphite, diatomaceous earth, white clay, fumed silica, settling silica,silicic anhydride, carbon black, calcium carbonate, clay, talc, titaniumoxide, magnesium carbonate, quartz, fine aluminum powder, flint powder,and zinc powder. Of these, more preferable ones are thixotropic fillers,e.g., settling silica, fumed silica and carbon black; and calciumcarbonate, titanium oxide and talc. The filler, when used, isincorporated preferably at about 10 to 500 parts by weight per 100 partsby weight of the silyl-containing ethylene/α-olefin/non-conjugatedpolyene random copolymer rubber (A1), more preferably about 20 to 300parts by weight.

The aging inhibitors useful for the present invention include commonlyused known ones, e.g., sulfur-based ones, radical inhibitors andultraviolet ray absorbers.

The sulfur-based aging inhibitors useful for the present inventioninclude mercaptans, salts thereof, sulfides including sulfidecarboxylate esters and hindered phenol-based sulfides, polysulfides,dithiocarboxylates, thioureas, thiophosphates, sulfonium compounds,thioaldehydes, thioketones, mercaptals, mercaptols, monothio acids,polythio acids, thioamides, and sulfoxides.

More concretely, the sulfur-based aging inhibitors include:

mercaptans, e.g., 2-mercaptobenzothiazole;

salts of mercaptans, e.g., zinc salt of 2-mercaptobenzothiazole;

sulfides, e.g., 4,4′-thio-bis (3-methyl-6-t-butyl phenol),4,4′-thio-bis(2-methyl-6-t-butyl phenol),2,2′-thio-bis(4-methyl-6-t-butyl phenol),bis(3-methyl-4-hydroxy-5-t-butylbenzyl)sulfide, terephthaloyldi(2,6-dimethyl-4-t-butyl-3-hydroxybenzyl)sulfide, phenothiazine,2,2′-thio-bis (4-octyl phenol)nickel, dilauryl thiodipropionate,distearyl thiodipropionate, dimyristyl thiodipropionate, ditridecylthiodipropionate, distearyl β,β-thiodibutyrate, lauryl-stearylthiodipropionate and 2,2-thio[diethyl-bis-3-(3,5-di-t-butyl-4-hydroxyphenol)propionate];

polysulfides, e.g., 2-benzothiazole disulfide;

dithiocarboxylates, e.g., zinc dibutyldithiocarbamate, zincdiethyldithiocarbamate, nickel dibutyldithiocarbamate, zincdi-n-butyldithiocarbamate, dibutyl ammonium dibutyldithiocarbamate, zincethyl-phenyl-dithiocarbamate and zinc dimethyldithiocarbamate;

thioureas, e.g., 1-butyl-3-oxy-diethylene-2-thiourea,di-o-tolyl-thiourea and ethylene thiourea; and

thiophosphates, e.g., trilauryltrithiophosphate.

The above-described sulfur-based aging inhibitor preventsdecomposition/aging of the main chain under heating much moreefficiently than the other types for the curable rubber composition ofthe present invention, controlling the problems, e.g., residual surfacetackiness.

The radical inhibitors useful for the present invention includephenol-based ones, e.g., 2,2-methylene-bis(4-methyl-6-t-butyl phenol)and tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane; and amine-based ones, e.g., phenyl-β-naphthylamine,α-naphthylamine, N,N′-sec-butyl-p-phenylenediamine, phenothiazine andN,N′-diphenyl-p-phenylenediamine.

The ultraviolet ray absorbers useful for the present invention include2-(2′-hydroxy-3′,5′-di-t-butylphenyl)benzotriazole andbis(2,2,6,6-tetramethyl-4-piperidine)cebacate.

The aging inhibitor, when used, is incorporated at about 0.1 to 20 partsby weight per 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1),preferably about 1 to 10 parts by weight.

A solvent may be used for, e.g., improving workability and reducingviscosity. The solvents useful for the above purposes include aromatichydrocarbon-based ones, e.g., toluene and xylene; ester-based ones,e.g., ethyl acetate, butyl acetate, amyl acetate and cellosolve acetate;and ketone-based ones, e.g., methylethylketone, methylisobutylketone anddiisobutylketone.

The tackifier composition (19) of the present invention can find wideuses, e.g., tapes, sheets, labels and foils. For example, theabove-described tackifier composition, of non-solvent liquid, solvent,emulsion or hot-melt type, is applied to a base material, e.g.,synthetic resin or modified natural film, paper, any type of cloth,metallic foil metallized plastic foil, asbestos or cloth of glassfibers, and cured at normal or elevated temperature after being exposedto moisture or water.

Tackifier Composition (19) and its Uses

The tackifier composition (19) of the present invention contains thetackifier composition with the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber as thecomponent (A1), as described earlier. More concretely, it contains theorganic polymer (Z), and a tackiness imparting resin (W) and curingcatalyst (H) composed of a specific organozirconium compound (H1) or aspecific organoaluminum compound (H2). It can be suitably used forelectric/electronic device members, transportation machines, and civilengineering/construction, medical and leisure areas, as describedearlier.

For the civil engineering/construction areas, the tackifier composition(19) can find uses for, e.g., adhesive, waterproof andvibration-preventive sheets, among others.

Rubber Composition (20)

The rubber composition (20) of the present invention contains thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1), and a specific curing catalyst (H).

[Curing Catalyst (H)]

The curing catalyst (H) is composed of a mercaptide type organotincompound (H3) having the Sn—S bond, a sulfide type organotin compound(H4) having the Sn═S bond, an organocarboxylic acid (H5), anorganocarboxylic anhydride (H6), or a mixture of one of the abovecompounds with carboxylic type organotin compound (H7).

For example, the mercaptide type organotin compound (H3) having the Sn—Sbond include those represented by the following formulae:

organotin compounds having an R₂Sn(—S . . . COO—) type ring, e.g.,

organotin compounds having an R₂Sn(—S . . . S—) type ring, e.g.,

R₂Sn(—SCH₂COOR)₂ type organotin compounds, e.g.,(n-C₄H₉—)₂Sn(—SCH₂COO-iso-C₈H₁₇)₂ and(n-C₈H₁₇—)₂Sn(—SCH₂COO-n-C₁₂H₂₅)₂;RSn(—SCH₂COOR)₃ type organotin compounds, e.g.,(n-C₄H₉—)Sn(—SCH₂COO-iso-C₈H₁₇)₃ and(n-C₈H₁₇—)Sn(—SCH₂COO-n-C₁₂H₂₅)₃.

The sulfide type organotin compounds (H4) having the Sn═S bond includean R₂Sn═S type one, e.g.,(n-C₈H₁₇—)₂Sn═S.

The organocarboxylic acids (H5) include benzoic, phthalic, succinic,adipic, pyromellitic, formic and acetic acids.

The organocarboxylic anhydrides (H6) include acetic, maleic, phthalic,succinic and dipyromellitic anhydrides.

The carboxylic type organotin compounds (H7) to be mixed with one of theabove-described (H3) to (H6) compounds for use of the curing catalyst(H) include those represented by the formulaSn(—OCO-n-C₈H₁₇)₂, e.g.,(n-C₄H₉—)₂Sn(—OCO-n-C₁₁H₂₃)₂,(n-C₄H₉—)₂Sn(—OCOCH═CHCOOCH₃)₂,(n-C₈H₁₇—)₂Sn(—OCO-n-C₁₁H₂₃)₂ and(n-C₈H₁₇—)₂Sn(—OCOCH═CHCOO-n-C₄H₉)₂.The tin (IV) compound is more preferable than the tin (II) compound forthe present invention.

For the present invention, the ratios of the mercaptide type organotincompound (H3) having the Sn—S bond to the carboxylic type organotincompound (H7), i.e., (H3)/(H7) ratio, of the sulfide type organotincompound (H4) having the Sn═S bond to the carboxylic type organotincompound (H7), i.e., (H4)/(H7) ratio, of the organocarboxylic acid (H5)to the carboxylic type organotin compound (H7), i.e., (H5)/(H7) ratio,and of the organocarboxylic anhydride (H6) to the carboxylic typeorganotin compound (H7), i.e., (H6)/(H7) ratio are each 0.1 to 20,preferably 0.1 to 10.

The curing catalyst (H) is incorporated at around 0.01 to 10 parts byweight per 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1),preferably 0.1 to 10 parts by weight. The curing catalyst gives therubber composition of improved pot life in an open atmosphere, when usedat a content in the above range.

Other Components

The rubber composition (20) of the present invention may beincorporated, as required, with at least one of the compounds selectedfrom the group consisting of trialkyl orthoformates, hydrolyzableorganosilicone compounds, hydrolyzable ester compounds and alkylalcohols within limits not detrimental to the object of the presentinvention.

The trialkyl orthoformates useful for the present invention includetrimethyl orthoformate and triethyl orthoformate.

The hydrolyzable organosilicone compounds useful for the presentinvention include tetramethyl orthosilicate and tetraethylorthosilicate.

The hydrolyzable ester compounds useful for the present inventioninclude methyltriethoxysilane, methyltriacetoxysilane and vinyltrimethoxysilane.

The alkyl alcohols useful for the present invention include methylalcohol, butyl alcohol, amyl alcohol and cellosolve.

The rubber composition of the present invention may be furtherincorporated with one or more additives, e.g., various types of fillers,pigments and plasticizers within limits not detrimental to the object ofthe present invention.

The fillers and pigments useful for the present invention includevarious types of silica, calcium carbonate, magnesium carbonate,titanium oxide, iron oxide and glass fibers.

The plasticizers useful for the present invention include process oil,paraffin oil, naphthene oil, polybutadiene and ethylene/α-olefinoligomer. The plasticizer may be used in place of the solvent during theprocess of introducing a hydrolyzable silyl group into the

-   -   ethylene/α-olefin/non-conjugated polyene random copolymer rubber        (A₀), for the purposes of, e.g., adjusting reaction temperature        and viscosity of the reaction system.

Rubber Composition (20) and its Uses

The rubber composition (20) of the present invention contains thecurable composition with the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber as thecomponent (A1), as described earlier. More concretely, it contains theorganic polymer (Z) and a specific curing catalyst (H), composed of amercaptide type organotin compound (H3) having the Sn—S bond, sulfidetype organotin compound (H4) having the Sn═S bond, organocarboxylic acid(H5), organocarboxylic anhydride (H6), or mixture of one of the abovecompounds and carboxylic type organotin compound (H7). It can besuitably used for electric/electronic device members, transportationmachines, and civil engineering/construction, medical and leisure areas,as described earlier.

The rubber composition (20) of the present invention can be used assealants, potting agents, coating materials or adhesives forelectric/electronic device members, transportation machines, and civilengineering/construction, and leisure areas.

Curable Composition (21)

The curable composition (21) of the present invention contains thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1) and a specific curing catalyst (H8)

Curing Catalyst (H8)

The copolymer rubber (A1) is crosslinked/cured by the condensation, whenits hydrolyzable silicon group is hydrolyzed in the presence ofmoisture. The curing catalyst (H8) for the present invention works togreatly promote curing of the copolymer rubber (A1).

For the curing catalyst (H8), a compound represented by the generalformula Q₂Sn(OZ)₂ or [Q₂Sn(OZ)]₂O is used, wherein Q is a monovalenthydrocarbon group of 1 to 20 carbon atoms; and Z is a monovalenthydrocarbon group of 1 to 20 carbon atoms or an organic group having afunctional group capable of forming therein a coordination bond with Sn.The concrete examples of these compounds include, but not limited to:

These curing catalysts (H8) may be used either individually or incombination. The curing catalyst (H8) is incorporated normally at 0.01to 10 parts by weight per 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1),preferably 0.1 to 5 parts by weight. At below 0.01 part, it may not curethe composition (21) at a practical speed, and it may cause cost-relatedproblems at above 10 parts.

The curing catalyst (H8) for the present invention notably promotes thequick-curing activity as compared with the organotin-based compound,which has been traditionally used, causes no coloration of thecomposition, unlike an alkyl titanate-based compound used as thecatalyst, and is excellent not only in productivity but also in externalappearances.

The curable composition (21) of the present invention, containing thecomponents (A1) and (H8), cures very fast, starting to cure from thesurface in several minutes to 1 hour when left in air at roomtemperature, becoming tack-free. When left for a couple of days, it iscured deep inside, turning into a solid rubber-like elastomer. The curedproduct is excellent in resistance to heat and acid.

Other Components

The copolymer rubber (A1) for the present invention can be modified,when incorporated with various types of fillers.

The fillers useful for the present invention include reinforcingfillers, e.g., fumed silica, settling silica, silicic anhydride, silicichydrate and carbon black; other fillers, e.g., calcium carbonate,magnesium carbonate, diatomaceous earth, fired clay, clay, talc,titanium oxide, bentonite, organic bentonite, ferric oxide, zinc oxide,activated zinc white, hydrogenated castor oil and silas balloons; andfibrous fillers, e.g., asbestos and glass fibers or filaments.

Of these, the one, mainly selected from the group consisting of fumedsilica, settling silica, silicic anhydride, silicic hydrate, carbonblack, surface-treated fine calcium carbonate, fired clay, clay andactivated zinc white is used when the curable composition of highstrength is to be produced. The filler will bring about the favorableeffect, when incorporated at 1 to 100 parts by weight per 100 parts byweight of the copolymer rubber as the component (A1). On the other hand,when the cured product of low strength and high elongation is to beproduced, the filler, mainly selected from the group consisting oftitanium oxide, calcium carbonate, magnesium carbonate, talc, ferricoxide, zinc oxide and silas balloons is used. It will bring about thefavorable effect, when incorporated at 5 to 200 parts by weight per 100parts by weight of the copolymer rubber as the component (A1). It isneedless to say that these fillers may be used either individually or incombination.

When incorporated with a plasticizer in combination with the filler, thecurable component (21) of the present invention will have one or moreadditional advantages, e.g., further improved elongation of the curedproduct and a larger quantity of the filler being incorporated.

The concrete examples of these plasticizers include phthalate esters,e.g., those of dibutyl phthalate, diheptyl phthalate,di(2-ethylhexyl)phthalate, butyl benzyl phthalate and butyl phthalylbutyl glycolate; non-aromatic, dibasic acid esters, e.g., those ofdioctyl adipate and dioctyl cebacate; esters of polyalkylene glycol,e.g., those of diethylene glycol dibenzoate and triethylene glycoldibenzoate; phosphate esters, e.g., those of tricresyl phosphate andtributyl phosphate; paraffin chlorides; and hydrocarbon-based compounds,e.g., alkyl diphenyl, polybutene, hydrogenated polybutene,ethylene/α-olefin oligomer, α-methyl styrene oligomer, biphenyl,triphenyl, triaryl dimethane, alkylene triphenyl, liquid polybutadiene,hydrogenated liquid polybutadiene, paraffin oil, naphthene oil, atacticpolypropylene and partially hydrogenated ter-phenyl. They may be usedeither individually or in combination. The plasticizer may beincorporated while the polymer is being produced.

Of these, hydrocarbon-based compounds free of unsaturated group, e.g.,hydrogenated polybutene, hydrogenated liquid polybutadiene, paraffinoil, naphthene oil and atactic polypropylene, are more preferable forvarious reasons, e.g., high compatibility with each component for thecurable composition (21) of the present invention, limited effects oncuring speed of the curable composition, good resistance to weather ofthe curable product, and cheapness.

The plasticizer may be used in place of the solvent during the processof introducing a reactive silicon group into the saturatedhydrocarbon-based polymer, for the purposes of, e.g., adjusting reactiontemperature and viscosity of the reaction system.

The plasticizer will bring about the favorable effect, when incorporatedat 100 parts by weight or less per 100 parts by weight of the component(A1).

The method of preparing the curable composition (21) of the presentinvention is not limited. It may be prepared by the common method, e.g.,kneading these components by, e.g., a mixer, roll or kneader at normalor elevated temerature, or mixing them after dissolving each componentin a small quantity of an adequate solvent. Each component can beadequately combined with the others mainly to produce a two-liquid typecomposition.

The curable composition (21) of the present invention is cured by theactions of moisture, when exposed to air, into a solid withthree-dimensional network structure to have rubber-like elasticity.

The curable composition (21) of the present invention may be adequatelyincorporated, as required, with one or more additives, when it is used.The additives useful for the present invention include another type ofcuring catalyst (e.g., lauryl amine or lead octylate), adhesionimporver, property adjuster, storage stability improver, ultraviolet rayabsorber, metal deactivator, ozone-caused aging inhibitor, lightstabilizer, amine-based radical chaining inhibitor, phosphorus-basedperoxide decomposer, lubricant, pigment, and foaming agent.

The concrete examples of the other curing catalysts useful for thepresent invention include titanate esters, e.g., those of tetrabutyltitanate and tetrapropyl titanate; organoaluminum compounds, e.g.,aluminum trisacetylacetonate, aluminum trisethylacetoacetate anddiisopropoxy aluminum ethylacetoacetate; chelate compounds, e.g.,zirconium tetraacetylacetonate and titanium tetraacetylacetonate; leadoctylate; amine-based compounds, and salts of these compounds andcarboxylates, e.g., butylamine, octylamine, laurylamine, dibutylamine,monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine,triethylenetetramine, oleylamine, cyclohexylamine, benzylamine,diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine,diphenylguanidine, 2,4,6-tris (dimethylaminomethyl)phenol, morpholine,N-methyl morpholine, 2-ethyl-4-methylimidazole and1,8-diazabicyclo(5,4,0)undecene-7 (DBU); low-molecular-weight polyamideresins produced by the reactions between excessive quantities ofpolyamines and polybasic acids; products of the reactions betweenexcessive quantities of polyamines and epoxy compounds; silane couplingagents containing amino group, e.g., γ-aminopropyl trimethoxy silane andN-(β-aminoethyl)aminopropyl methyldimethoxy silane; and other knownsilanol condensing catalysts, acidic or basic.

The adhesion improvers useful for the present invention include commonlyused adhesives, silane coupling agents, e.g., aminosilane and epoxysilane compounds; and others.

The concrete examples of these adhesion improvers include phenolicresin, epoxy resin, γ-aminopropyl trimethoxysilane,N-(β-aminoethyl)aminopropyl methyldimethoxysilane, coumarone/indeneresin, rosin ester resin, terpene/phenol resin, α-methyl styrene/vinyltoluene copolymer, polyethylmethyl styrene, alkyl titanate, and aromaticpolyisocyanate.

The storage stability improvers useful for the present invention includecompounds with silicon to which a hydrolyzable group is bonded, andesters of ortho-organic acids.

The concrete examples of the storage stability improvers includemethyltrimethoxy silane, methyltriethoxy silane, tetramethoxy silane,ethyltrimethoxy silane, dimethyldiethoxy silane, trimethylisobutoxysilane, trimethyl(n-butoxy)silane, n-butyltrimethoxy silane, and methylorthoformate.

The aging inhibitors useful for the present invention include commonlyused known ones, e.g., sulfur-based ones, radical inhibitors andultraviolet ray absorbers.

The sulfur-based aging inhibitors useful for the present inventioninclude mercaptans, salts thereof, sulfides including sulfidecarboxylate esters and hindered phenol-based sulfides, polysulfides,dithiocarboxylates, thioureas, thiophosphates, sulfonium compounds,thioaldehydes, thioketones, mercaptals, mercaptols, monothio acids,polythio acids, thioamides, and sulfoxides.

The concrete examples of the sulfur-based aging inhibitors includemercaptans, e.g., 2-mercaptobenzothiazole; salts of mercaptans, e.g.,zinc salt of 2-mercaptobenzothiazole; sulfides, e.g.,4,4′-thio-bis(3-methyl-6-t-butyl phenol),4,4′-thio-bis(2-methyl-6-t-butyl phenol),2,2′-thio-bis(4-methyl-6-t-butyl phenol),bis(3-methyl-4-hydroxy-5-t-butylbenzyl)sulfide, terephthaloyldi(2,6-dimethyl-4-t-butyl-3-hydroxybenzyl)sulfide. phenothiazine,2,2′-thio-bis(4-octyl phenol)nickel, dilauryl thiodipropionate,distearyl thiodipropionate, dimyristyl thiodipropionate, ditridecylthiodipropionate, distearylβ,β′-thiodibutyrate, lauryl-stearylthiodipropionate and 2,2-thio[diethyl-bis-3-(3,5-di-t-butyl-4-hydroxyphenol)propionate]; polysulfides, e.g., 2-benzothiazole disulfide;dithiocarboxylates, e.g., zinc dibutyldithiocarbamate, zincdiethyldithiocarbamate, nickel dibutyldithiocarbamate, zincdi-n-butyldithiocarbamate, dibutyl ammonium dibutyldithiocarbamate, zincethyl-phenyl-dithiocarbamate and zinc dimethyldithiocarbamate;thioureas, e.g., 1-butyl-3-oxy-diethylene-2-thiourea,di-o-tolyl-thiourea and ethylene thiourea; and thiophosphates, e.g.,trilauryltrithiophosphate.

The sulfur-based aging inhibitor prevents decomposition/aging of themain chain under heating much more efficiently than the other types forthe composition of the present invention, controlling the problems,e.g., residual surface tackiness.

The radical inhibitors useful for the present invention includephenol-based ones, e.g., 2,2-methylene-bis(4-methyl-6-t-butyl phenol)and tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane; and amine-based ones, e.g., phenyl-β-naphthylamine,α-naphthylamine, N,N′-sec-butyl-p-phenylenediamine, phenothiazine andN,N′-diphenyl-p-phenylenediamine.

The ultraviolet ray absorbers useful for the present invention include2-(2′-hydroxy-3′,5′-di-t-butylphenyl)benzotriazole andbis(2,2,6,6-tetramethyl-4-piperidine)cebacate.

Curable Composition (21) and its Uses

The curable composition (21) of the present invention contains thecurable composition with the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber as thecomponent (A1), as described in detail earlier. More concretely, itcontains the organic polymer (Z) and curing catalyst (H8). It can besuitably used for electric/electronic device members, transportationmachines, and civil engineering/construction, medical and leisure areas,as described earlier.

The curable composition (21) of the present invention can be used assealants, potting agents, coating materials or adhesives forelectric/electronic device members, transportation machines, and civilengineering/construction, and leisure areas.

In other words, the present invention provides sealants, potting agents,coating materials and adhesives, composed of the curable compositioncontaining the organic polymer (Z) and curing catalyst (H8).

Curable Rubber Composition (22)

The curable rubber composition (22) of the present invention containsthe silyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1), titanates (Y) and, as required, a silanolcondensing catalyst.

Titanates (Y)

The titanate (Y) for the present invention is a characteristic componentfor the present invention which improves adhesion strength of theethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1)containing a hydrolyzable silyl group to various types of bases, e.g.,glass, metal and mortar. Moreover, it works as the silanol condensingcatalyst which promotes the silanol condensation of hydrolyzable silylgroups with each other in the ethylene/α-olefin/non-conjugated polyenerandom copolymer rubber (A1) containing a hydrolyzable silyl group.

The titanates (Y) useful for the present invention includeorganotitanate esters, chelate compounds of titanium and silicate estersof titanium, titanate-based coupling agents, and partially hydrolyzedcondensates thereof.

The concrete examples of the titanates (Y) useful for the presentinvention include tetra-iso-propyl titanate, tetra-normal-butyltitanate, butyl titanate dimer, tetrakis(2-ethylhexyl)titanate,tetrastearyltitanate, tetramethyl titanate,diethoxybis(acetylacetonato)titanium,di-iso-propylbis(acetylacetonato)titanium,di-iso-propoxybis(ethylacetoacetate)titanium,iso-propoxy(2-ethyl-1,3-hexanediolato)titanium,di(2-ethylhexoxy)bis(2-ethyl-1,3-hexanediolato)titanium,di-n-butoxybis(triethanolaminato)titanium, tetraacetylacetonatetitanium, hydroxybis(lactato)titanium, and hydrolysis condensatesthereof.

The concrete examples of the titanate-based coupling agents useful forthe present invention include the compounds represented by the followingformulae, and hydrolysis condensates thereof:

Of the above-described titanates (Y), those represented by the followinggeneral formula are more preferable, because of their especially higheffect of improving adhesion:Ti(OR)₄wherein, R's are each a hydrocarbon group of 1 to 20 carbon atoms, whichmay be substituted or not substituted.

These titanates (Y) may be used either individually or in combination.

The titanate (Y) is incorporated preferably at 0.1 to 20 parts by weightper 100 parts by weight of the component (A1), particularly preferably 1to 10 parts by weight. It may not exhibit sufficient effect of improvingadhesion at below 0.1 part, and may deteriorate storage stability of thesealant composition at above 20 parts by weight.

Silanol Condensing Catalysts

A silanol condensing catalyst may be used for the curable rubbercomposition (22) of the present invention. The silanol condensingcatalysts useful for the present invention include divalent ortetravalent tin-based, aluminum-based and amine-based curing catalysts.Of these catalysts, the tetravalent tin-based ones are more preferablefor their high catalytic activity. The tetravalent tin-based curingcatalyst and the concrete examples are similar to those of thetetravalent tin compound (C) as the one constituent component for thecurable rubber composition (2) described earlier.

The silanol condensing catalysts, other than the tetravalent tin-basedcuring catalyst, maybe used for the present invention.

The concrete examples of these catalysts useful for the presentinvention include divalent tin-based curing catalysts, e.g., tinoctylate, aluminum-based curing catalysts, e.g., aluminumtrisacetylacetonate, aluminum trisethylacetoacetate and diisopropoxyaluminum ethylacetoacetate; zirconium tetraacetylacetonate; leadoctylate; amine-based curing catalysts, e.g., butylamine, octylamine,laurylamine, dibutylamine, monoethanolamine, diethanolamine,triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine,cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine,triethylenediamine, guanidine, diphenylguanidine,2,4,6-tris(dimethylaminomethyl)phenol, morpholine, N-methyl morpholine,2-ethyl-4-methylimidazole and 1,8-diazabicyclo(5,4,0)undecene-7 (DBU),and salts of these compounds and carboxylates; low-molecular-weightpolyamide resins produced by the reactions between excessive quantitiesof polyamines and polybasic acids; products of the reactions betweenexcessive quantities of polyamines and epoxy compounds; silane couplingagents containing amino group, e.g., γ-aminopropyltrimethoxysilane andN-(β-aminoethyl)aminopropyl methyldimethoxy silane; and other knowncatalysts, acidic or basic.

These catalysts may be used either individually or in combination. Thesilanol condensing catalyst is incorporated preferably at 0.1 to 20parts by weight per 100 parts by weight of the component (A1),particularly preferably 1 to 10 parts by weight. The catalyst contentbelow the above range is undesirable, because of insufficient curingspeed and insufficient extent of the curing reaction, and beyond theabove range is also undesirable, because of local heating or foamingoccurring during the curing process to make it difficult to produce thecured product of good properties, and also may deteriorate its pot lifeto an unacceptable level and workability of the composition.

Other Components

The silyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1) is itself relatively high in viscosity, and maysometimes cause workability-related problems. It is therefore a goodpractice to incorporate a various type of plasticizer in the copolymerrubber to an extent not harmful to adhesion of the curable rubbercomposition (22) of the present invention, in order to reduce itsviscosity and thereby to improve its handleability.

The plasticizer useful for the present invention is not limited, and anycommonly used one may be used. Preferably, it should be compatible witheach component for the silyl-containing ethylene/α-olefin/non-conjugatedpolyene random copolymer rubber (A1) of the present invention.

The concrete examples of these plasticizers include: phthalate esters,e.g., those of dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl)phthalate, butyl benzyl phthalate, and butyl phthalyl butyl glycolate;non-aromatic, dibasic acid esters, e.g., those of dioctyl adipate anddioctyl cebacate;

esters of polyalkylene glycol, e.g., those of diethylene glycol benzoateand triethylene glycol dibenzoate; phosphate esters, e.g., those oftricresyl phosphate and tributyl phosphate; paraffin chlorides; andhydrocarbon-based compounds, e.g., alkyl diphenyl, polybutene,hydrogenated polybutene, hydrogenated α-olefin oligomer,ethylene/α-olefin oligomer, α-methyl styrene oligomer, biphenyl,triphenyl, triaryl dimethane, alkylene triphenyl, liquid polybutadiene,hydrogenated liquid polybutadiene, paraffin oil, naphthene oil, atacticpolypropylene and partially hydrogenated ter-phenyl. They may be usedeither individually or in combination. The plasticizer may beincorporated while the polymer is being produced.

Of these compounds, hydrocarbon-based compounds free of unsaturatedgroup, e.g., hydrogenated polybutene, hydrogenated liquid polybutadiene,hydrogenated α-olefin oligomer, paraffin oil, naphthene oil and atacticpolypropylene, are more preferable for various reasons, e.g., highcompatibility with each component for the rubber composition (22) of thepresent invention, limited effects on curing speed of the rubbercomposition, good resistance to weather of the cured product, andcheapness.

The plasticizer may be used in place of the solvent during the processof introducing a reactive silyl group into the above-describedethylene/α-olefin/non-conjugated polyene random copolymer rubber, forthe purposes of, e.g., adjusting reaction temperature and viscosity ofthe reaction system. The plasticizer is incorporated preferably at 10 to150 parts by weight per 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1),particularly preferably 30 to 100 parts by weight. The plasticizer maynot sufficiently exhibit the effect of reducing viscosity at below 10parts, whereas it may deteriorate mechanical and adhesion properties ofthe composition at above 150 parts by weight. The curable rubbercomposition (22) of the present invention may be further incorporatedwith a varying aging inhibitor.

The aging inhibitors useful for the present invention includephenol-based antioxidants, aromatic amine-based antioxidants,sulfur-based hydroperoxide decomposers, phosphorus-based hydroperoxidedecomposers, benzotriazole-based ultra violet ray absorbers,salicylate-based ultraviolet ray absorbers, benzophenone-basedultraviolet ray absorbers, hindered amine-based light stabilizers andnickel-based light stabilizers.

The concrete examples of the phenol-based antioxidants include2,6-di-t-butyl phenol, 2,4-di-t-butyl phenol, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butylhydroquinone,n-octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate,pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate],2,2′-methylenebis(4-methyl-6-t-butyl phenol),4,4′-butylidenebis(3-methyl-6-t-butyl phenol) and4,4′-thiobis(3-methyl-6-t-butyl phenol).

The concrete examples of the aromatic amine-based antioxidants includeN,N′-diphenyl-p-phenylenediamine and6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline.

The concrete examples of the sulfur-based hydroxyperoxide decomposersinclude dilauryl-3,3′-thiodipropionate, ditridecyl-3,3′-thiodipropionateand distearyl-3,3′-thiodipropionate.

The concrete examples of the phosphorus-based hydroxyperoxidedecomposers include diphenylisooctyl phosphite and triphenyl phosphite.

The concrete examples of the benzotriazole-based ultraviolet rayabsorbers include2-(3,5-di-t-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole,2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazol e,2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole and2-(5-methyl-2-hydroxyphenyl)benzotriazole.

The concrete examples of the salicylate-based ultraviolet ray absorbersinclude 4-t-butylphenylsalicylate and2,4-di-t-butylphenyl-3,5′-di-t-butyl-4′-hydroxybenzoate.

The concrete examples of the benzophenone-based ultraviolet rayabsorbers include 2,4-dihydroxybenzophenone,2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone,2-hydroxy-4-n-dodecyloxybenzophenone and2-hydroxy-4-benzyloxybenzophenone.

The concrete examples of the hindered amine-based light stabilizersinclude bis(2,2,6,6-tetramethyl-4-piperidyl)cebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)cebacate,1-{2-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]ethyl}-4-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]-2,2,6,6-tetramethylpiperidineand 4-benzoyloxy-2,2,6,6-tetramethylpiperidine.

The concrete examples of the nickel-based light stabilizers includenickel dibutyldithiocarbamate,[2,2′-thiobis(4-t-octylphenolate)]-2-ethylhexylamine nickel (II) and[2,2′-thiobis(4-t-octylphenolate)]-n-butylamine nickel (II).

These aging inhibitors may be used either individually or incombination. They may exhibit their functions more efficiently when usedin combination than individually. In particular, a combination of aphenol-based antioxidant, a salicylate-based ultraviolet ray absorberand a hindered amine-based light stabilizer greatly improves weatherresistance of the silyl-containing ethylene/α-olefin/non-conjugatedpolyene random copolymer rubber as the component (A1), and hence isdesirable.

The aging inhibitor is incorporated preferably at 0.1 to 10 parts byweight per 100 parts by weight of the component (A1), particularlypreferably 0.5 to 5 parts by weight. It may not sufficiently improveresistance of the curable rubber composition to weather at below 0.1part, and may deteriorate its economics and adhesion at above 10 partsby weight.

The curable rubber composition (22) of the present invention isincorporated, as required, with a varying adhesion improver, other thanthe titanates (Y).

The adhesion improvers useful for the present invention include epoxyresin, phenol resin, various silane coupling agents and aromaticpolyisocyanates.

The concrete examples of the silane coupling agents useful for thepresent invention include

amino-containing silanes, e.g., γ-aminopropyltrimethoxysilane,γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane,γ-aminopropylmethyldiethoxysilane,γ-(2-aminoethyl)aminopropyltrimethoxysilane,γ-(2-aminoethyl)aminopropylmethyldimethoxysilane,γ-(2-aminoethyl)aminopropyltriethoxysilane,γ-(2-aminoethyl)aminopropylmethyldiethoxysilane,γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane,N-benzyl-γ-aminopropyltrimethoxysilane andN-vinylbenzyl-γ-aminopropyltriethoxysilane;

mercapto-containing silanes, e.g., γ-mercaptopropyltrimethoxysilane,γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilaneand γ-mercaptopropylmethyldiethoxysilane;

epoxy-containing silanes, e.g., γ-glycidoxypropyltrimethoxysilane,γ-glycidoxypropyltriethoxysilane,γ-glycidoxypropylmethyldimethoxysilane,β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane andβ-(3,4-epoxycyclohexyl)ethyltriethoxysilane;

carboxysilanes, e.g., β-carboxyethyltriethoxysilane,β-carboxyethylphenylbis (2-ethoxyethoxy)silane andN-β-(carboxymethyl)aminoethyl-γ-aminopropyltrimethoxysilane;

vinyl type unsaturated group-containing silanes; e.g.,vinyltrimethoxysilane, vinyltriethoxysilane,γ-methacryloyloxypropylmethyldimethoxysilane andγ-acryloyloxypropylmethyltriethoxysilane;

halogen-containing silanes, e.g., γ-chloropropyltrimethoxysilane;

silane isocyanurates, e.g., tris(trimethoxysilyl)isocyanurate; and

isocyanate-containing silanes, e.g., γ-isocyanatepropyltrimethoxysilane, γ-isocyanate propyltriethoxysilane, γ-isocyanatepropylmethyldiethoxysilane and γ-isocyanate propylmethyldimethoxysilane.

Moreover, the modifications of these compounds as their derivatives arealso useful as the silane coupling agents. These compounds includeamino-modified silyl polymers, silylated amino polymers, unsaturatedaminosilane complexes, block isocyanate silanes, phenylamino-longchain-alkyl silanes, aminosilylated silicone and silylated polyesters.

The silane coupling agent is incorporated preferably at 0.1 to 20 partsby weight per 100 parts by weight of the component (A1), particularlypreferably 1 to 10 parts by weight.

It may not exhibit sufficient effect of improving adhesion at below 0.1part, and may deteriorate storage stability of the sealant compositionat above 20 parts by weight. These silane coupling agents may be usedeither individually or in combination.

The curable rubber composition (22) of the present invention isincorporated, as required, with a various filler.

The concrete examples of the fillers include wood powder, pulp, cottonchips, asbestos, glass fibers, carbon fibers, mica, walnut shell powder,rice hull powder, graphite, diatomaceous earth, white clay, fumedsilica, settling silica, silicic anhydride, carbon black, calciumcarbonate, clay, talc, titanium oxide, magnesium carbonate, quartz, finealuminum powder, flint powder, and zinc powder. Of these, morepreferable ones are settling silica, fumed silica, carbon black, calciumcarbonate, titanium oxide and talc. They may be used either individuallyor in combination.

The filler is incorporated preferably at 5 to 500 parts by weight per100 parts by weight of the component (A1), particularly preferably 20 to350 parts, still particularly preferably 40 to 200 parts by weight.

The curable rubber composition (22) of the present invention may befurther incorporated, as required, with one or more additives, inaddition to the components (A) and (Y), silanol condensing catalyst, andplasticizer, aging inhibitor, adhesion improver and filler describedabove. The additives useful for the present invention include propertyadjuster which adjusts the tensile-related properties of the curedproduct, weather-resistant adhesion improver, radical inhibitor, metaldeactivator, ozone-caused aging inhibitor, dripping inhibitor,phosphorus-based peroxide decomposer, solvent, lubricant, pigment, andfoaming agent.

The concrete examples of these additives are described in, e.g.,Japanese Patent Publication Nos. 69659/1992 and 108928/1995, U.S. Pat.No. 2,512,468, and Japanese Patent Laid-Open Publication No. 22904/1989.

The effect of the titanates (Y) for the present invention is alsoobserved, even when various additives are incorporated. More concretely,the curable rubber composition (22) of the present invention, when usedas a sealant for construction works, laminated glass or a sealing agentfor rust-prevention or water-proof of edges (cut sections) of wired orlaminated glass, will have still improved adhesion of the sealant tovarious objects, when incorporated with the titanates (Y).

Curable Rubber Composition (22) and its Uses

The curable rubber composition (22) of the present invention containsthe curable composition with the ethylene/α-olefin/non-conjugatedpolyene random copolymer rubber containing a hydrolyzable silyl group asthe component (A1), as described in detail earlier. More concretely, thecurable rubber composition contains the organic polymer (Z) andtitanates (Y). It can be suitably used for electric/electronic devicemembers, transportation machines, and civil engineering/construction,medical and leisure areas, as described earlier.

The curable rubber composition may be further incorporated with theabove-described silanol condensing catalyst.

The curable rubber composition (22) of the present invention can be usedas sealants, potting agents, coating materials or adhesives forelectric/electronic device members, transportation machines, and civilengineering/construction, and leisure areas.

In other words, the present invention provides sealants, potting agents,coating materials and adhesives, composed of the curable compositioncontaining the organic polymer (Z) and titanates (Y).

The above-described sealants, potting agents, coating materials oradhesives may be further incorporated with the above-described silanolcondensing catalyst.

Curable Composition (23)

The curable composition (23) of the present invention contains thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1), and can be suitably used for electric/electronicdevice members, transportation machines, and civilengineering/construction, medical and leisure areas, as describedearlier.

The curable composition (23) of the present invention may be furtherincorporated, as required, with one or more additives, e.g., curingcatalyst, plasticizer and filler. The curing catalysts useful for thepresent invention are not limited, but common silanol condensingcatalysts may be used.

The concrete examples of the curing catalysts useful for the presentinvention include organotin, organotitanate, organoaluminum,organozirconium, amine compounds and acidic phosphate ester, andproducts by the reaction between an acidic phosphate ester and an aminecompound, saturated or unsaturated polyvalent carboxylic acids andanhydrides thereof, products by the reaction between salt of carboxylateand an amine compound, and lead octylate.

The concrete examples of the organotin compounds include tincarboxylates, e.g., dibutyl tin diacetate, dibutyl tin dilaurate,dibutyl tin maleate, dioctyl tin maleate, dibutyl tin phthalate, tinoctylate and tin naphthenate; chelate compounds, e.g., dibutyl tindiacetylacetonate; dibutyl tin methoxide; and products of the reactionsbetween dibutyl tin oxides and phthalate esters.

The concrete examples of the organotitanate compounds include titanateesters, e.g., those of tetrabutyl titanate, tetraisopropyl titanate,tetrapropyl titanate and triethanolamine titanate; and chelatecompounds, e.g., titanium tetraacetylacetonate.

The concrete examples of the organoaluminum compounds include aluminumtrisacetylacetonate, aluminum trisethylacetoacetate and diisopropoxyaluminum ethylacetoacetate.

The concrete examples of the organozirconium compounds includeorganozirconium compounds, e.g., zirconium tetraisopropoxide andzirconium tetrabutoxide, and chelate compounds, e.g., zirconiumtetraacetylacetonate.

The concrete examples of the amine compounds include butylamine,monoethanolamine, triethylenetriamine, guanidine,2-ethyl-4-methylimidazole and 1,8-diazabicyclo(5,4,0)undecene-7 (DBU).

The acidic phosphate esters mean the phosphate esters containing theportion of —O—P (═O)(OH)—. The examples are acidic phosphate esters,such as organic acidic phosphate esters represented by the generalformula;(RO)_(d)—P(═O)—(OH)_(3-d),wherein, “d” is 1 or 2; and R is an organic residue.

The organic acidic phosphate esters include the following compounds:(CH₃O)₂P(═O)OH,(CH₃O)P(═O)(OH)₂,(C₂H₅O)₂P(═O)OH,(C₂H₅O)P(═O)(OH)₂,[(CH₃)₂CHO)₂P(═O)OH,(CH₃)₂CHOP(═O)(OH)₂,(C₄H₉O)₂P(═O)OH,(C₄H₉O)P(═O)(OH)₂,(C₈H₁₇O)₂P(═O)OH,(C₈H₁₇O)P(═O)(OH)₂,(C₁₀H₂₁O)₂P(═O)OH,(C₁₀H₂₁O)P(═O)(OH)₂,(C₁₃H₂₇O)₂P(═O)OH,(C₁₃H₂₇O)P(═O)(OH)₂,(HOC₈H₁₆)₂P(═O)OH,(HOC₈H₁₆O)P(═O)(OH)₂,(HOC₆H₁₂O)₂P(═O)OH,(HOC₆H₁₂O)P(═O)(OH)₂,[(CH₂OH)(CHOH)O]₂P(═O)OH,[(CH₂OH)(CHOHO)O]—P(═O)—(OH)₂,[(CH₂OH)(CHOH)C₂H₄O]₂P(═O)OH and[(CH₂OH)(CHOH)C₂H₄O]P(═O)(OH)₂.

The curing catalyst is incorporated at around 0 to 20 parts by weightper 100 parts by weight of the hydrolyzable silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1).

The plasticizer useful for the present invention is not limited, and anycommonly used one may be used. Preferably, it should be compatible witheach component for the curable composition (23) of the presentinvention. The concrete examples of these plasticizers include phthalateesters, e.g., those of dibutyl phthalate, diheptyl phthalate,di(2-ethylhexyl)phthalate, butyl benzyl phthalate and butyl phthalylbutyl glycolate; non-aromatic, dibasic acid esters, e.g., those ofdioctyl adipate and dioctyl cebacate;

-   -   esters of polyalkylene glycol, e.g., those of diethylene glycol        dibenzoate and triethylene glycol dibenzoate; phosphate esters,        e.g., those of tricresyl phosphate and tributyl phosphate;        paraffin chlorides; and hydrocarbon-based compounds, e.g., alkyl        diphenyl, polybutene, hydrogenated polybutene, ethylene/α-olefin        oligomer, α-methyl styrene oligomer, biphenyl, triphenyl,        triaryl dimethane, alkylene triphenyl, liquid polybutadiene,        hydrogenated liquid polybutadiene, paraffin oil, naphthene oil,        atactic polypropylene and partially hydrogenated ter-phenyl.        They may be used either individually or in combination. The        plasticizer may be incorporated while the polymer is being        produced.

Of these compounds, hydrocarbon-based compounds free of unsaturatedgroup, e.g., hydrogenated polybutene, hydrogenated liquid polybutadiene,paraffin oil, naphthene oil and atactic polypropylene, are morepreferable for various reasons, e.g., high compatibility with eachcomponent for the composition (23) of the present invention, limitedeffects on curing speed of the curable composition, good resistance toweather of the cured product, and cheapness.

The plasticizer may be used in place of the solvent during the processof introducing a reactive silicon group into the saturatedhydrocarbon-based polymer, for the purposes of, e.g., adjusting reactiontemperature and viscosity of the reaction system.

The plasticizer will bring about the favorable effect when incorporatedat 100 parts by weight or less per 100 parts by weight of the component(A1).

The concrete examples of the fillers include inorganic fillers, e.g.,calcium carbonate, talc, diatomaceous earth, mica, kaolin, magnesiumcarbonate, vermiculite, titanium oxide, graphite, alumina, silica, glassballoons, silas balloons, silica balloons, calcium oxide, magnesiumoxide and silicon oxide; and organic fillers, e.g., powdered rubber,recycled rubber, fine powders of thermosetting or thermoplastic resins,and hollow particles of polyethylene and the like. The filler isincorporated at around 3 to 300 parts by weight per 100 parts by weightof the silyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1).

The aging inhibitors useful for the present invention include commonlyused known ones, e.g., sulfur-based ones, radical inhibitors andultraviolet ray absorbers.

The sulfur-based aging inhibitors useful for the present inventioninclude mercaptans, salts thereof, sulfides including sulfidecarboxylate esters and hindered phenol-based sulfides, polysulfides,dithiocarboxylates, thioureas, thiophosphates, sulfonium compounds,thioaldehydes, thioketones, mercaptals, mercaptols, monothio acids,polythio acids, thioamides, and sulfoxides.

The concrete examples of the sulfur-based aging inhibitors includemercaptans, e.g., 2-mercaptobenzothiazole; salts of mercaptans, e.g.,zinc salt of 2-mercaptobenzothiazole; sulfides, e.g.,4,4′-thio-bis(3-methyl-6-t-butyl phenol),4,4′-thio-bis(2-methyl-6-t-butyl phenol),2,2′-thio-bis(4-methyl-6-t-butyl phenol),bis(3-methyl-4-hydroxy-5-t-butylbenzyl)sulfide, terephthaloyldi(2,6-dimethyl-4-t-butyl-3-hydroxybenzyl)sulfide, phenothiazine,2,2′-thio-bis(4-octylphenol)nickel, dilauryl thiodipropionate, distearylthiodipropionate, dimyristyl thiodipropionate, ditridecylthiodipropionate, distearyl β,β′-thiodibutyrate, lauryl-stearylthiodipropionate and 2,2-thio[diethyl-bis-3-(3,5-di-t-butyl-4-hydroxyphenol)propionate]; polysulfides, e.g., 2-benzothiazole disulfide;dithiocarboxylates, e.g., zinc dibutyldithiocarbamate, zincdiethyldithiocarbamate, nickel dibutyldithiocarbamate, zincdi-n-butyldithiocarbamate, dibutyl ammonium dibutyldithiocarbamate, zincethyl-phenyl-dithiocarbamate and zinc dimethyldithiocarbamate;thioureas, e.g., 1-butyl-3-oxy-diethylene-2-thiourea,di-o-tolyl-thiourea and ethylene thiourea; and thiophosphates, e.g.,trilauryltrithiophosphate.

The sulfur-based aging inhibitor prevents decomposition/aging of themain chain under heating much more efficiently than the other types forthe composition of the present invention, controlling the problems,e.g., residual surface tackiness.

The radical inhibitors useful for the present invention includephenol-based ones, e.g., 2,2-methylene-bis(4-methyl-6-t-butyl phenol)and tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane; and amine-based ones, e.g., phenyl-β-naphthylamine,α-naphthylamine, N,N′-sec-butyl-p-phenylenediamine, phenothiazine andN,N′-diphenyl-p-phenylenediamine.

The ultraviolet ray absorbers useful for the present invention include2-(2′-hydroxy-3′,5′-di-t-butylphenyl)benzotriazole andbis(2,2,6,6-tetramethyl-4-piperidine)cebacate.

The aging inhibitor, when used, is incorporated preferably at around 0.1to 20 parts by weight per 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1),more preferably 1 to 10 parts by weight.

The other additives useful for the present invention include dippinginhibitors, e.g., hydrogenated castor oil, organic bentonite and calciumstearate; colorants, tackifiers and solvents.

The curable composition (23) thus produced to contain the component (A1)is useful as a coating material, in particular as a coating material forunderbodies and a sealant for bodies of vehicles for rust-prevention andvibration-insulation, and matches the requirements by the recentautomobile industry.

Curable Composition (23) and its Uses

The curable composition (23) of the present invention containing thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber as the component (A1) can be suitably used forelectric/electronic device members, transportation machines, and civilengineering/construction, medical and leisure areas, as describedearlier. It is particularly useful as a coating material for vehicles,and other purposes.

For example, the curable composition (23) of the present invention canbe suitably used as sealants, potting agents, coating materials forpurposes other than vehicles or adhesives for electric/electronic devicemembers, transportation machines, and civil engineering/construction,and leisure areas.

The curable composition (23) of the present invention is incorporated inthe coating material (23)′ for vehicles, sealant (24)′, potting material(24)′ and coating material (24)′ for purposes other than vehicles andadhesive (24)′, all of the present invention.

Sealant (25)′ for Laminated Glass

The sealant(25)′ of the present invention for laminated glass containsthe silyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A2), curing catalyst (H) and water or hydrate of ametallic salt (B11).

The sealant (25)′ of the present invention for laminated glass containsthe silyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A2) preferably at 5 to 50% by weight, particularlypreferably 5 to 40% by weight.

The curing catalyst (H) for the present invention may be a known silanolcondensing catalyst. The concrete examples of the curing catalystsuseful for the present invention are described earlier.

The curing catalyst (H) is incorporated preferably at 0.1 to 20 parts byweight per 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A2),more preferably 1 to 10 parts by weight. The catalyst content below theabove range may cause insufficient curing speed and insufficient extentof the curing reaction. The content beyond the above range is alsoundesirable, because it may cause local heating or foaming occurringduring the curing process to make it difficult to produce the curedproduct of good properties, which may deteriorate pot life to anunacceptable level and workability of the composition.

Water or hydrate of a metallic salt (B11) for the present inventionfunctions as the source of water necessary for condensing/curing of thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A2), and promotes formation of the crosslinkedstructure.

When the water source is other than water, widely varying commoncommercial hydrates of metals can be used. These hydrates include thoseof alkali-earth metals and other metals. Of these, the more preferableones are those of alkali and alkali-earth metals. More concretely, theyinclude MgSO₄.7H₂O, Na₂CO₃.10H₂O, Na₂SO₄.10H₂O, Na₂S₂O₃.5H₂O,Na₃PO₄.12H₂O and Na₂B₄O₇.10H₂O.

Water as the component (B11) is incorporated preferably at 0.01 to 25parts by weight per 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A2),more preferably 0.05 to 15 parts, still more preferably 0.2 to 5 partsby weight.

A hydrate of metallic salt as the component (B11) is incorporatedpreferably at 0.01 to 50 parts by weight per 100 parts by weight of thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A2), more preferably 0.1 to 30 parts, still morepreferably 1 to 10 parts by weight.

Water and hydrates of metallic salts may be used either individually orin combination.

The sealant (25)′ of the present invention for laminated glass may beincorporated with various additives.

The representative additive is a tackifier, which is represented by asilane coupling agent. It is needless to say that a tackifier other thansilane coupling agent may be used. The silane coupling agent is acompound which has a group containing the silicon atom to which ahydrolyzable group is bonded (hereinafter referred to as hydrolyzablesilicon group) and one or more other functional groups. The hydrolyzablegroup is preferably methoxy, ethoxy or the like viewed from hydrolysisspeed. It preferably has 2 or more hydrolyzable groups, still morepreferably 3 or more.

The functional groups useful for the present invention, other than thehydrolyzable silicon groups, include primary, secondary and tertiaryamino, mercapto, epoxy, carboxyl, vinyl, isocyanate, isocyanurate, andhalogen. Of these, primary, secondary or tertiary amino, epoxy,isocyanate and isocyanurate are more preferable, and isocyanate andepoxy are still more preferable.

The concrete examples of the silane coupling agents useful for thepresent invention include:

amino-containing silanes, e.g., γ-aminopropyltrimethoxysilane,γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane,γ-(2-aminoethyl)aminopropyltrimethoxysilane,γ-(2-aminoethyl)aminopropylmethyldiemethoxysilane,γ-(2-aminoethyl)aminopropyltriethoxysilane,γ-(2-aminoethyl)aminopropyltriethoxysilane,γ-ureidopropyltrimethoxysilane,n-β-(n-vinylbenzylaminoethyl)-γ-aminopropyltriethoxysilane andγ-anilinopropyltrimethoxysilane;

mercapto-containing silanes, e.g., γ-mercaptopropyltrimethoxysilane,γ-mercaptopropyltriethoxysilane, γ-mercaptopropylethyldimethoxysilaneand γ-mercaptopropylmethyldiethoxysilane;

epoxy-containing silanes, e.g., γ-glycidoxypropyltrimethoxysilane,γ-glycidoxypropyltriethoxysilane,γ-glycidoxypropylmethyldimethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltriethoxysilane;

carboxysilanes, e.g., β-carboxyethyltriethoxysilane,β-carboxyethylphenylbis (2-methoxyethoxy)silane andn-β-(n-carboxymethylaminoethyl)-γ-aminopropyltrimethoxysilane;

vinyl type unsaturated group-containing silanes; e.g.,vinyltrimethoxysilane, vinyltriethoxysilane,γ-methacryloyloxypropylmethyldimethoxysilane andγ-acryloyloxypropylmethyltriethoxysilane;

halogen-containing silanes, e.g., γ-chloropropyltrimethoxysilane;

silane isocyanurates, e.g., tris(trimethoxysilyl)isocyanurate; and

isocyanate-containing silanes, e.g., γ-isocyanate propyltrimethoxysilaneand γ-isocyanate propyltriethoxysilane.

Moreover, the modifications of these compounds as their derivatives arealso useful as the silane coupling agents. These compounds includeamino-modified silyl polymers, silylated amino polymers, unsaturatedaminosilane complexes, block isocyanate silanes, phenylamino-longchain-alkyl silanes, aminosilylated silicone and silylated polyesters.These silane coupling agents tend to be hydrolyzed easily in thepresence of moisture, but can be kept stable when incorporated in thecomponent (A2) for the sealant (25)′ of the present invention forlaminated glass.

The tackifiers, other than a silane coupling agent, useful for thepresent invention include commonly used adhesives, and other compounds.The concrete examples of these tackifiers include phenolic resin, epoxyresin, coumarone/indene resin, rosin ester resin, terpene/phenol resin,α-methyl styrene/vinyl toluene copolymer, polyethylmethyl styrene, alkyltitanate, and aromatic polyisocyanate.

The tackifier is incorporated at 0.01 to 20 parts by weight per 100parts by weight of the silyl-containing ethylene/α-olefin/non-conjugatedpolyene random copolymer rubber (A2), particularly preferably 0.1 to 10parts by weight. These tackifiers may be used either individually or incombination.

The sealant (25)′ of the present invention for laminated glass may befurther incorporated with a varying type of filler, to still improve itsproperties. The fillers useful for the present invention includereinforcing fillers, e.g., fumed silica, settling silica, silicicanhydride, silicic hydrate, talc and carbon black; other fillers, e.g.,limestone powder, colloidal calcium carbonate, diatomaceous earth, firedclay, clay, titanium oxide, bentonite, organicbentonite, ferric oxide,zinc oxide and activated zinc white; and fibrous fillers, e.g., glassfibers or filaments.

Of these, the reinforcing filler, mainly of fumed silica, settlingsilica, silicic anhydride, silicic hydrate, talc or carbon black, isused when the curable sealant of high strength is to be produced. Thecured product of good mechanical properties in terms of strength andmodulus can be prepared, when it is incorporated at 1 to 100 parts byweight per 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A2).

On the other hand, when the cured product of low modulus and highelongation is to be produced, it is recommended to incorporate the othertype of filler, e.g., limestone powder, colloidal calcium carbonate,diatomaceous earth, fired clay, clay, titanium oxide, bentonite,organicbentonite, ferric oxide, zinc oxide or activated zinc white, at 5to 400 parts by weight per 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A2).

It is needless to say that these fillers may be used either individuallyor in combination.

The filler may be incorporated in the silyl-containing

-   -   ethylene/α-olefin/non-conjugated polyene random copolymer rubber        (A2), curing catalyst as the component (H), or both.

When incorporated with a plasticizer in combination with the filler, thesealant (25)′ of the present invention for laminated glass will have oneor more additional advantages, e.g., further improved elongation of thecured product and a larger quantity of the filler being incorporated.

For the plasticizer, any commonly used one may be used. Preferably, itshould be compatible with the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A2).

The concrete examples of the plasticizers include process oil,polybutene, hydrogenated polybutene, α-methyl styrene oligomer, liquidpolybutadiene, hydrogenated liquid polybutadiene, paraffin oil,naphthene oil and atactic polypropylene. Of these, more preferable onesare the hydrocarbon-based compounds free of unsaturated group, e.g.,process oil, hydrogenated polybutene, hydrogenated liquid polybutadiene,paraffin oil and naphthene oil.

The plasticizer may be used in place of the solvent during the processof introducing a reactive silicon group into theethylene/α-olefin/non-conjugated polyene copolymer rubber, for thepurposes of, e.g., adjusting reaction temperature and viscosity of thereaction system.

The plasticizer, when used, is incorporated preferably at around 10 to500 parts by weight per 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A2),more preferably around 20 to 300 parts by weight.

The sealant (25)′ of the present invention for laminated glass may beadequately incorporated, as required, with various additives, e.g.,aging inhibitor, light stabilizer, flame retardant, thixotropy enhancer,pigment and surfactant.

The aging inhibitors useful for the present invention include commonlyused known ones, e.g., sulfur-based ones, radical inhibitors andultraviolet ray absorbers.

The sulfur-based aging inhibitors useful for the present inventioninclude mercaptans, salts thereof, sulfides including sulfidecarboxylate esters and hindered phenol-based sulfides, polysulfides,dithiocarboxylates, thioureas, thiophosphates, sulfonium compounds,thioaldehydes, thioketones, mercaptals, mercaptols, monothio acids,polythio acids, thioamides, and sulfoxides.

The concrete examples of the sulfur-based aging inhibitors includemercaptans, e.g., 2-mercaptobenzothiazole; salts of mercaptans, e.g.,zinc salt of 2-mercaptobenzothiazole; sulfides, e.g.,4,4′-thio-bis(3-methyl-6-t-butyl phenol),4,4′-thio-bis(2-methyl-6-t-butyl phenol),2,2′-thio-bis(4-methyl-6-t-butyl phenol),bis(3-methyl-4-hydroxy-5-t-butylbenzyl)sulfide, terephthaloyldi(2,6-dimethyl-4-t-butyl-3-hydroxybenzyl)sulfide, phenothiazine,2,2′-thio-bis(4-octyl phenol)nickel, dilauryl thiodipropionate,distearyl thiodipropionate, dimyristyl thiodipropionate, ditridecylthiodipropionate, distearyl β,β′-thiodibutyrate, lauryl-stearylthiodipropionate and 2,2-thio[diethyl-bis-3-(3,5-di-t-butyl-4-hydroxyphenol)propionate]; polysulfides, e.g., 2-benzothiazole disulfide;dithiocarboxylates, e.g., zinc dibutyldithiocarbamate, zincdiethyldithiocarbamate, nickel dibutyldithiocarbamate, zincdi-n-butyldithiocarbamate, dibutyl ammonium dibutyldithiocarbamate, zincethyl-phenyl-dithiocarbamate and zinc dimethyldithiocarbamate;thioureas, e.g., 1-butyl-3-oxy-diethylene-2-thiourea,di-o-tolyl-thiourea and ethylene thiourea; and thiophosphates, e.g.,trilauryltrithiophosphate.

The sulfur-based aging inhibitor prevents decomposition/aging of themain chain under heating much more efficiently than the other types forthe rubber composition of the present invention, controlling theproblems, e.g., residual surface tackiness.

The radical inhibitors useful for the present invention includephenol-based ones, e.g., 2,2-methylene-bis(4-methyl-6-t-butyl phenol)and tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane; and amine-based ones, e.g., phenyl-β-naphthylamine,α-naphthylamine, N,N′-sec-butyl-p-phenylenediamine, phenothiazine andN,N′-diphenyl-p-phenylenediamine.

The ultraviolet ray absorbers useful for the present invention include2-(2′-hydroxy-3′,5′-di-t-butylphenyl)benzotriazole andbis(2,2,6,6-tetramethyl-4-piperidine)cebacate.

The aging inhibitor, when used, is incorporated preferably at around 0.1to 20 parts by weight per 100 parts by weight of the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A2),more preferably around 1 to 10 parts by weight.

Sealant (26)′ for Laminated Glass

The sealant (26)′ of the present invention for laminated glass containsthe silyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A2), a hot melt resin (X), a curing catalyst (H) andwater or a hydrate of a metallic salt (B11).

The silyl-containing ethylene/(α-olefin/non-conjugated polyene randomcopolymer rubber (A2), being a hydrocarbon-based polymer, shows goodmoisture shielding and water-proof properties, is highly adhesive tovarious inorganic base materials, e.g., glass and aluminum, and givesthe cured product which shields moisture well.

The sealant (26)′ of the present invention for laminated glass containsthe ethylene/α-olefin/non-conjugated polyene random copolymer rubber(A2) preferably at 5 to 50% by weight, more preferably 10 to 50%, inorder to secure a sufficient tackiness (initial adhesion) to temporarilytack a spacer to glass in the laminated glass production line.

The hot melt resin (X) for the present invention is not limited, andcommon commercial ones can be used. These include, for example, EVA-,polyamide-, polyester-, polyurethane-, acrylic-, butyl rubber- andpolyolefin-based hot melt resins.

The hot melt resin preferably has a softening temperature of around 100to 250° C. viewed from workability, although not limited thereto.

The more preferable ones include butyl rubber-based hot melt resins (hotmelt butyl). The hot melt butyl useful for the present invention is notlimited, and common, commercial ones can be used. They may be free ofadditives, or incorporated with one or more of additives, e.g., filler.Those useful for the present invention include butyl rubber having anunsaturation degree of around0.5to5.0 (IIR), Vistanex Series (ExxonMobil) Terostat Series (Teroson) and Hamatite Series (Yokohama Rubber)

The hot melt resin (X) for the present invention, e.g., hot melt butyl,is directly used without being vulcanized.

The sealant (26)′ of the present invention for laminated glass containsthe hot melt resin (X) preferably at 20 to 95% by weight, morepreferably 50 to 90%, in order to secure a sufficient tackiness (initialadhesion) to temporarily tack a spacer to glass in the laminated glassproduction line.

The curing catalyst (H) is incorporated preferably at 0.1 to 20 parts byweight per 100 parts by weight of the component (A2), more preferably 1to 10 parts, in order to prevent local heating or foaming, and secure anadequate pot life at an adequate curing speed.

Water as the component (B11) is incorporated preferably at 0.01 to 25parts by weight per 100 parts by weight of the component (A2), morepreferably 0.05 to 15 parts by weight, still more preferably 0.2 to 5parts.

The hydrate of a metallic salt as the component (B11) is incorporatedpreferably at 0.01 to 50 parts by weight per 100 parts by weight of thecomponent (A2), more preferably 0.1 to 30 parts by weight, still morepreferably 1 to 10 parts.

Water and the hydrates of metallic salts as the component (B11) may beused either individually or in combination.

Effects of the Invention

(1) The curable elastomer composition (1) of the present inventioncontains the curable composition with the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber as thecomponent (A1), as described in detail earlier. More concretely, itcontains the organic polymer (Z) containing a specific hydrolyzablesilyl group and essentially no unsaturated double bond in the mainchain, and the compound (B1) having a silanol group and/or the compoundwhich can react with moisture to form a compound having a silanol groupin the molecule. As such, it improves elongation and residual tackinesson the surface of the cured product, is cured quickly, and gives thecured product high in resistance to weather.

Therefore, the curable elastomer composition (1) of the presentinvention is suitable for adhesives, tackifiers, paints, sealants,waterproof materials, spray materials, shaping materials and castingrubber materials.

(2) The curable rubber composition (2) of the present invention containsthe ethylene/α-olefin/non-conjugated polyene random copolymer rubber(A1) containing a specific silyl group. More concretely, it contains theorganic polymer (Z) containing a specfic hydrolyzable silyl group andessentially no unsaturated double bond in the main chain, a tetravalenttin compound (C) and a specific silicon compound (B2). As such, it ishighly resistant to weather, cured quickly, and can greatly improveadhesion to various objects. When incorporated with various additives,the curable rubber composition (2) of the present invention can befurther improved in adhesion to various base materials.

The curable rubber composition (2) of the present invention isparticularly useful for an elastomer sealant particularly required to becured very quickly, e.g., a sealant for laminated glass, and anelectrical insulator, e.g., an insulating coating material for wires andcables.

(3) The present invention can provide the curable composition (3), curedquickly, and excellent in residual tackiness, resistance to weather andadhesion to paints.

(4)The curable composition (4) of the present invention can form arubber-like elastomer, good in storage stability, high in curing speed,excellent in tensile properties, free of residual tackiness, andexcellent in resistance to weather.

(5) The rubber composition (5) of the present invention curable atnormal temperature contains the silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1) orthe organic polymer (Z) containing a specific hydrolyzable silyl groupand essentially no unsaturated double bond in the main chain, and aspecific silane compound (B5). As such, it is cured quickly andexcellent in resistance to weather, and can give the cured product(cured coating film) excellent in adhesion.

The rubber composition (5) of the present invention curable at normaltemperature is particularly adhesive to the coating film of conventionalpaints, e.g., those of melamine alkyd and melamine acrylic resin, andsuitably used for, e.g., paints for repairing automobiles.

(6) The curable rubber composition (6) of the present invention containsthe ethylene/α-olefin/non-conjugated polyene random copolymer rubber(A1) having a specific hydrolyzable silyl group or the organic polymer(Z) containing a specific hydrolyzable silyl group and essentially nounsaturated double bond in the main chain, specific amines (D) and aspecific silane coupling agent (B6). As such, it can be easily curedwith moisture in air at normal temperature or under heating withoutaffecting adversely the properties of its cured product. It can be curedquickly, and gives the cured product (cured coating film) excellent inresistance to weather.

Therefore, the curable rubber composition (6) of the present inventioncan find wide uses for paints curable at normal temperature or underheating, in particular those suitable for repairing automobiles, new carproduction lines, precoated metals, glass, rust-prevention of heavystructures (e.g., bridges) and construction materials, and also forcoating materials, adhesives and sealants.

(7) The curable composition (7) of the present invention is curedquickly, and gives the cured product of greatly improved adhesivestrength and weather-resistance adhesion while keeping its modulus low.

(8) The curable composition (8) of the present invention is curedquickly, and can greatly improve adhesive strength andweather-resistance adhesion of the cured product while keeping itsmodulus low. It also shows excellent characteristics in storagestability.

(9) The curable rubber composition (9) of the present invention containsthe silyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1) or the organic polymer (Z) containing a specifichydrolyzable silyl group and essentially no unsaturated double bond inthe main chain, alcohols (B9) and/or a hydrolyzable ester compound (I),a hydrolyzable organosilicon compound (B10), and, as required, a curingpromoter. As such, it is excellent in storage stability and curedquickly, and can give the cured product excellent in resistance toweather.

The curable rubber composition (9) of the present invention is usefulfor paints, and quickly cured at normal temperature to give coatingfilms of very excellent surface gloss. Incorporation of ethyl silicatein the ethylene/α-olefin/non-conjugated polyene random copolymer rubber(A1) allows to freely adjust surface hardness of the coating film.

Moreover, the curable rubber composition (9) of the present invention isuseful not only for paints but also for coating compositions for, e.g.,aircraft, buildings and automobiles, sealant compositions andsurface-treating agents for various inorganic materials.

(10) The curable rubber composition (10) of the present inventioncontains water or a hydrate of metallic salt as the source of waternecessary for the curing reaction, together with a silanol condensingcatalyst. The composition shows essentially no deterioration incurability (curing speed) after being stored, and is high in curingspeed and excellent in resistance to weather. Moreover, the curablerubber composition (10) of the present invention can be incorporatedwith a compound having a reactive silicon group readily reactive withmoisture, e.g., a silane coupling agent. It shows little crosslinkingreaction while being stored, which prevented from increasing inviscosity.

(11) The rubber composition (11) of the present invention contains theethylene/α-olefin/non-conjugated polyene random copolymer rubber (A2)containing the hydrolyzable silyl group represented by theabove-described formula (1) in the molecule, and an organosilicon polmer(K1). As such, it is well workable and cured sufficiently quickly, andgives the cured product excellent in various characteristics, e.g.,resistance to weather, heat and water, and strength and elongation.Incorporation of a polysiloxane having 2 or more silanol groups bringsabout an advantage of very high curability deep inside of thecomposition. Therefore, the rubber composition (11) of the presentinvention is particularly suitable for sealants, adhesives, paints,waterproof materials, spray materials, shaping materials and castingrubber materials.

(12)The rubber composition (12) of the present invention contains theethylene/α-olefin/non-conjugated polyene random copolymer rubber (A2)containing the hydrolyzable silyl group represented by theabove-described formula (1) in the molecule, an organic rubber (K2) anda crosslinking agent (M) for the organic rubber (K2). As such, it isvulcanized quickly, and gives the vulcanized curable rubber elastomerexcellent in various characteristics, e.g., resistance to weather, heatand chemicals, and mechanical strength. Therefore, it is particularlysuitable for hoses, vibration insulators, belts, coupling agents,weather strips, glass channels, cable coatings, condenser-sealingrubber, water-proof materials, sealants, adhesives, sealants forlaminated glass, and formed articles, e.g., shoe soles.

(13) The present invention can give not only the cured product excellentin adhesion, greatly changed in the layered structure, and low inelasticity and high in elongation, but also the one high in modulus ofelasticity and tensile shear strength by decreasing size of the epoxyresin particles dispersed therein and increasing content of the epoxyresin in the matrix. The rubber composition (13) of the presentinvention can be cured sufficiently quickly, and give the cured producthigh in resistance to weather.

(14)The present invention provides a high-strength cured product,improved in toughness and strength without being affected by moisturequantity. The curable rubber composition (14) of the present inventioncan be cured sufficiently quickly, and give the cured product high inresistance to weather.

(15) The curable rubber composition (15) of the present inventioncontains the ethylene/α-olefin/non-conjugated polyene random copolymerrubber (A2) containing the hydrolyzable silyl group represented by theabove-described formula (1) in the molecule, calcium carbonate (L1) andtalc (L2). As such, it is well balanced between workability andmechanical characteristics of the cured product, cured sufficientlyquickly, and gives the cured product excellent in resistance to weather.Therefore, it is suitably used as a sealant for laminated glass, andalso for other purposes, e.g., elastomer sealants for construction, andsealing materials for SSG construction method, rust-prevention orwater-proof of edges (cut sections) of wired or laminated glass.

(16)The curable composition (16) of the present invention exhibits goodweather-resistant adhesion even to a transparent object for which theconventional composition is difficult to exhibit weather-resistantadhesion, e.g., various types of surface-treated heat ray reflectiveglass. Moreover, it is cured quickly, and gives the cured product ofhigh resistance to weather.

(17) The curable rubber composition (17) of the present invention iscured quickly, high in resistance to weather, and gives the curedproduct of high resistance to heat.

The curable rubber composition (17) of the present invention is suitablyused for adhesives, tackifiers, paints, sealant compositions, waterproofagents, spray materials, shaping materials and casting rubber materials.

(18) The curable composition (18) of the present invention is curedquickly, and greatly improved in adhesion to various objects and variousglassy base materials, in particular in weather-resistant adhesion toheat ray reflective glass. It is also excellent in resistance toweather. When incorporated with various additives, the curablecomposition (18) of the present invention is particularly useful forelastomer sealants, e.g., those for laminated glass and SSG constructionmethod, which are required to be adhesive to various objects andweather-resistant adhesive to glassy base materials.

(19)The tackifier composition (19) of the present invention contains thesilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1) or the organic polymer (Z) containing ahydrolyzable silyl group and essentially no unsaturated double bond inthe main chain, a specific curing catalyst (H1 or H2) for the condensingreaction between the groups having the hydrolyzable silicon in thecomponent (Z), and tackiness imparting resin (W). As such, it isexcellent in releasability for silicon releasing paper or film, curedquickly, and excellent in resistance to weather.

The tackifier composition (19) of the present invention is applicable tothe products required to be releasable from silicone releasing paper orfilm, e.g., double-faced tapes, labels and sheets.

(20) The rubber composition (20) of the present invention contains theethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1)having a hydrolyzable silyl group at the terminal or in the side chainor the organic polymer (Z) containing a specific hydrolyzable silylgroup and essentially no unsaturated double bond in the main chain, anda specific curing catalyst (one of H3 to H7). As such, it can be greatlyimproved in pot life in an open atmosphere, and is cured quickly andexcellent in resistance to weather.

The rubber composition (20) of the present invention is curable atnormal or low temperature, and hence it is useful for paints or coatingmaterials.

Moreover, the rubber composition (20) of the present invention can beblended with various resins used for traditional paints and coatingmaterials, e.g., lacquer-, acrylic lacquer-, thermosetting acrylic,alkyd, melamine and epoxy resins in an adequate ratio. When blended, itcan be improved in properties, e.g., adhesion and resistance to weather,of the traditional paints and coating materials.

Still moreover, the rubber composition (20) of the present invention isuseful for coating and sealant compositions for, e.g., aircraft,structures, automobiles and glass, and surface-treating agents forvarious inorganic materials.

(21)The curable composition (21) of the present invention, comprisingthe specific copolymer rubber as the component (A1) and a specificcuring catalyst as the component (H8), is cured notably quicker than theconventional curable composition. It is also greatly improved inresistance to weather.

The curable composition (21) of the present invention, exhibiting theabove effects, is useful not only for tackifiers and sealants, but alsofor adhesives, shaping materials, vibration insulators, foamingmaterials, paints and spray materials.

(22) The curable rubber composition (22) of the present invention isexcellent in resistance to weather, and can be greatly improved incuring speed and adhesion to various objects. When incorporated withvarious additives, the curable rubber composition (22) of the presentinvention is particularly useful for elastomer sealants, e.g., those forlaminated glass and SSG construction method, which are required to beadhesive to various objects.

(23) The curable composition (23) of the present invention can besuitably used for electric/electronic device members, transportationmachines, and civil engineering/construction, medical and leisure areas,particularly useful as a coating material (23)′ for vehicles, and alsofor other purposes, e.g., sealants, potting agents and coating materialsfor purposes other than vehicles, and adhesives, all falling into thecompositions.

(23)′ The coating material of the present invention for vehicles canmeet the requirements by the automobile industry for decreasing weightof vehicles, and saving resources and energy by decreasing temperatureand time for baking. Moreover, it can be made into thin films which showexcellent rust prevention, vibration insulation and resistance toweather, even when prepared under curing conditions of low temperatureand short time.

(25)′ The sealant of the present invention for laminated glass containsthe ethylene/α-olefin/non-conjugated polyene random copolymer rubber(A2) having, in the molecule, a hydrolyzable silyl group represented bythe general formula (1), a curing catalyst (H) and water or a hydrate ofa metallic salt (B11). As such, it has various favorablecharacteristics, e.g., resistance to weather and heat,non-contaminating, low moisture-permeation, weather-resistant adhesion,and low odor. Moreover, it is excellent in mechanical characteristics,and can be produced at low cost.

(26)′ The sealant of the present invention for laminated glass containsthe ethylene/α-olefin/non-conjugated polyene random copolymer rubber(A2) having, in the molecule, a hydrolyzable silyl group represented bythe general formula (1), a hot melt resin (X), a curing catalyst (H) andwater or a hydrate of a metallic salt (B11). As such it is improved independence of its structural strength on temperature and in adhesion toa base material as compared with the conventional hot melt resin, whilekeeping its steam impermeability. Therefore, it is suitably used as aprimary sealant for dual sealing or a sealant for single sealing forlaminated glass.

EXAMPLES

The present invention is explained by EXAMPLES which by no means limitthe present invention.

Examples A Series

The composition, iodine value, intrinsic viscosity [η] and molecularweight distribution (Mw/Mn) of the copolymer rubber used in each ofEXAMPLES and COMPARATIVE EXAMPLES were determined by the followingmethods.

(1) Composition of the Copolymer Rubber

Composition of the copolymer rubber was determined by the ¹³C-NMRmethod.

(2) Iodine Value of the Copolymer Rubber

Iodine value of the copolymer rubber was determined by the titrationmethod.

(3) Intrinsic Viscosity [η]

Intrinsic viscosity [η] of the copolymer rubber was measured in decalinkept at 135° C.

(4) Molecular Weight Distribution (Mw/Mn)

Molecular weight distribution (Mw/Mn) of the copolymer rubber wasdefined as ratio of weight-average molecular weight (Mw) tonumber-average molecular weight (Mn), both determined by GPC with GMH-HTor GMH-HTL (TOSOH CORP.) as the column and orthodichlorobenzene as thesolvent.

The curing speed tests and accelerated weather resistance tests wereconducted by the following methods for EXAMPLES and COMPARATIVE EXAMPLES

(1) Curing Speed Test

The curable composition (stock material) was cured under the conditionsof 50° C. and 50% RH (relative humidity) for 24 hours in a mold, 20 by80 by 5 mm in size.

Next, the cured product was released from the mold, and thickness of thecured portion was measured by a dial gauge of weak spring force to 0.1mm, to evaluate its curing speed. It was marked with ⊚ when itsthickness was 1 mm or more, Δ when it was 0.5 to 1 mm, and x when it wasless than 0.5 mm.

(2) Accelerated Weather Resistance Test

The weather resistance test was conducted in accordance with JIS B-7753using a Sunshine Carbon Arc weatherometer.

<Testing Conditions>

-   Light irradiation/rainfall cycles: Irradiation for 120    minutes/rainfall for 18 minutes-   Black panel temperature: 63±2° C.-   Tank inside temperature: 40±2° C.-   Total light irradiation time: 250 hours

Production Example

[Production of silyl-containing ethylene/propylene/5-vinyl-2-norborneneRandom Copolymer Rubber (A-1)]

The three-component copolymerization was effected continuously in astainless steel polymerization reactor having an essential capacity of100 L, equipped with agitator blades (agitating rotation speed: 250rpm), wherein hexane, ethylene, propylene and 5-vinyl-2-norbornene werecontinuously supplied at 60 L, 2.5 kg, 4.0 kg and 380 g per hour,respectively, from the reactor side into the liquid phase, and hydrogen,VO(OEt)₂Cl and Al (Et)_(1.5)Cl_(1.5) as the catalysts at 700 L, 45 mmolsand 315 mmols per hour, respectively, also continuously.

The copolymerization effected under the above conditions produced theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A₀-1)in a form of uniform solution.

A small quantity of methanol was added to the polymer solution,continuously withdrawn from the reactor bottom, in order to terminatethe polymerization. The polymer was separated from the solvent bysteam-stripping the solution, and dried at 55° C. for 48 hours under avacuum.

The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber(A₀-1) thus produced contained ethylene at 68% by mol, and had anintrinsic viscosity [η] of 0.2 dl/g measured in decalin kept at 135° C.,iodine value (IV) of 10(g/100 g) and Mw/Mn of 15.

Two % toluene solution (0.3 g) of chloroplatinic acid and 1.5 g ofmethyldimethoxysilane were added to 100 g of theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A₀-1),and they were allowed to react with each other at 120° C. for 2 hours.The excess methyldimethoxysilane and the solvent (toluene) weredistilled off from the effluent. This produced 101.5 g of theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1)containing dimethoxymethylsilyl group(—SiCH₃(OCH₃)₂).

Reference Example A1

n-Butyl acrylate 128 g (1 mol), 0.74 g (0.005 mols) of vinyltrimethoxysilane and 1.44 g (0.008 mols) ofγ-mercaptopropylmethyldimethoxysilane were mixed with each other, towhich 0.3 g of α,α′-azobisisobutylonitrile was added to be dissolvedtherein with stirring. A portion (30 g) of the mixed solution was put ina 300 ml, 4-mouthed flask equipped with a condenser, drip-feed funneland agitator, after it was purged with dried nitrogen gas, and heated ina nitrogen atmosphere by an oil bath (80° C.). The polymerizationstarted in a couple of minutes to generate heat and thicken the mixedsolution. The remaining mixed solution was added dropwise through thefunnel, after the heat generation calmed down, and the mixed solutionwas totally added in about 3 hours. Sixty mL of 20% (by weight) acetonesolution of α,α′-azobisisobutylonitrile was added 15 minutes and then 30minutes after the addition of the mixed solution was completed, and thesolution was stirred for another 30 minutes under heating, to terminatethe polymerization. The polymer thus produced was colorless, transparentand viscous, had a viscosity of 890 poise at 23° C., contained theresidual monomer at 15% determined by gas chromatography, and had anaverage molecular weight of 21,000 measured by gel permeationchromatography (GPC).

Rererence Examples A2 to A7

The polymers were prepared in the same manner as in REFERENCE EXAMPLEA1, except that the components given in Table A1 were used. Viscosity,residual monomer content and average molecular weight of each polymerare given in Table A1.

TABLE A1 (Production of organic vinyl-based polymers) REFERENCE EXAMPLESA2 A3 A4 A5 A6 A7 Monomer as major BA BA BA BA BA BA ingredients (g)(50) (100) (128) (128) (128) (128) Other monomers (g) 2EHA VAc HDDA TMPANPCDA FA-731A (50) (20) (1.70) (1.78) (2.12) (4.24) MAPDMS MAPDMS MAPDMS(0.50) (0.50) (0.70) Chain transfer agent (g) MPTES MPDMS MPDMS MPDMSMPDMS MPDMS (5.50) (3.50) (1.70) (3.25) (3.61) (4.93) Polymerizationinitiator AIBN AIBN AIBN AIBN AIBN AIBN (g) (0.35) (0.35) (0.41) (0.41)(0.35) (0.35) Viscosity (poise at 23° C.)*1 180 230 670 350 250 430Residual monomer (%)*2 1.5 1.7 1.6 2.1 1.8 1.3 Average molecularweight*3 6000 8000 15000 10000 8000 12000 *1: Determined by a B typeviscometer *2: Determined by gas chromatography (internal standardmethod) *3: Determined by GPC BA: n-butyl acrylate 2EHA: 2-Ethylhexylacrylate VAc: Vinyl acetate HDDA: CH₂═CH—CO—O(CH₂)₆O—CO—CH═CH₂ TMPA:(CH₂═CH—CO—O)₃C—CH₂CH₃ NPCDA: CH₂═CH—CO—OCH₂—C(CH₃)₂—CH₂O—CO—CH═CH₂FA-731A:

MAPDMS: CH₂═C(CH₃)—CO—O(CH₂)₅—Si(OCH₃)₂(CH₃) MAPTMS:CH₂═C(CH₃)—CO—(CH₂)₅—Si(OCH₃)₃ MPDMS:γ-mercaptopropylmethyldimethoxysilane MPTES:γ-mercaptopropyltriethoxysilane AIBN: α,α′-azobisisobutylonitrile

Example A1

A mixture of 30 g of the silyl-containingethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1),prepared in PRODUCTION EXAMPLE, and 0.43 g of triphenyl silanol becamecompletely transparent and uniform, when stirred at 90° C. for 2 hours.As the curing catalyst, 0.9 g of NO918 (heat-treated 2:1 mixture ofdibutyl tin oxide and di-2-ethylhexyl phthalate, SANKYO ORGANICCHEMICALS) was added to the above mixture. The resultant mixture wassufficiently stirred for mixing, subjected to centrifugal defoaming at3,000 rpm for 10 minutes, and put in a polyethylene mold frame, 11 by 8by 0.3 cm, in which it was cured at room temperature for 3 days and at50° C. for 4 days. This produced a colorless, transparent cured sheetshowing rubber-like elasticity.

The cured sheet was punched into a dumbbells-shaped test piece (No. 3 inaccordance with JIS K-6301). It was subjected to the tensile test at atensile speed of 200 mm/minute by an Autograph, to determine itselongation breaking strength. The results are given in Table A2.

As shown in Table A2, incorporation of triphenyl silanol greatlyimproves the tensile characteristics, and can improve elongation of acured acrylic-based polymer which tends to show insufficient elongation.

Comparative Examples A1 to A23

A mixture of 30 g of the organic polymer (1), prepared in REFERENCEEXAMPLE A1, and0.43 g of triphenyl silanol was prepared for each ofCOMPARATIVE EXAMPLES. It became completely transparent and uniform, whenstirred at 90° C. for 2 hours. As the curing catalyst, 0.9 g of NO918(heat-treated 2:1 mixture of dibutyl tin oxide and di-2-ethylhexylphthalate, SANKYO ORGANIC CHEMICALS) was added to the above mixture. Theresultant mixture was sufficiently stirred for mixing, subjected tocentrifugal defoaming at 3,000 rpm for 10 minutes, and put in apolyethylene mold frame, 11 by 8 by 0.3 cm, in which it was cured atroom temperature for 3 days and at 50° C. for 4 days. This produced acolorless, transparent cured sheet showing rubber-like elasticity.

The cured sheet was punched into a dumbbells-shaped test piece (No. 3 inaccordance with JIS K-6301). It was subjected to the tensile test at atensile speed of 200 mm/minute by an Autograph, to determine itselongation breaking strength. The results are given in Table A2,together with those of the cured sheets free of triphenyl silanol.

The cured sheets were also prepared from the organic polymers (2) to (7)prepared in REFERENCE EXAMPLES A2 to A7, and tested. The results arealso given in Table A2, together with those of the cured sheets free oftriphenyl silanol.

As shown in Table A2, incorporation of triphenyl silanol greatlyimproves the tensile characteristics, and can improve elongation of acured acrylic-based polymer which tends to show insufficient elongation.

The cured sheets were prepared in the same manner as in COMPARATIVEEXAMPLE A1 except that triphenyl silanol was replaced by (CH₃)₂Si(OCH₃)₂(hereinafter referred to as the dimethoxy compound) or CH₂═CHSi(OCH₃)₃(hereinafter referred to as the trimethoxy compound) which can form acompound having 2 or more silanol groups in the molecule, to analyzetheir elongation and breaking strength. The results are given in TableA3 (COMPARATIVE EXAMPLES A8 to A15) and Table A4 (COMPARATIVE EXAMPLESA16 to A23).

It is found, when the results in Table A2 are compared with those inTables A3 and A4, that a compound having only one silanol group, e.g.,triphenyl silanol, greatly improves elongation of the cured sheet in apeculiar manner.

TABLE A2 COMPARATIVE EXAMPLES A1 A2 A3 A4 A5 A6 A7 EXAMPLE REFER- REFER-REFER- REFER- REFER- REFER- REFER- A1 ENCE ENCE ENCE ENCE ENCE ENCE ENCECopolymer rubber PRODUCTION EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLEEXAMPLE EXAMPLE or Polymer EXAMPLE A1 A2 A3 A4 A5 A6 A7 Triphenylsilanol0.43 0.43 0.39 0.29 0.38 0.45 0.71 0.24 Quantity (g) Triphenylsilanol 5050 20 25 40 40 50 15 Ratio (mol %)* Curing speed ⊚ X X X X X X XResistance to A B C C B B B C weather Elongation (%) 620 500 300 350 450520 350 250 Breaking 3.0 2.3 2.0 2.3 1.9 1.8 2.0 1.8 strength (kg/cm³)No Elongation 310 260 120 150 190 240 110 130 triphonyl- (%) silanolBreaking 2.9 2.5 2.1 2.3 2.1 1.8 2.2 1.9 added Strength (kg/cm³) *Mol %based on the silicon-containing compound used when the copolymer rubberor organic polymer is produced Evaluation of resistance to weather: A:No cracks or molten portion observed, B: Small cracks or molten portionobserved, although slightly, C: Cracks or molten portion observed.

TABLE A3 (Effects of incorporation of the dimethoxy compound)COMPARATIVE EXAMPLES A8 A9 A10 A11 A12 A13 A14 A15 Copolymer PRODUC-REFERENCE REFERENCE REFERENCE REFERENCE REFERENCE REFERENCE REFERENCErubber or TION EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLEpolymer EXAMPLE A1 A2 A3 A4 A5 A6 A7 Dimethoxy 0.21 0.21 0.17 0.13 0.170.20 0.31 0.10 compound Quantity (g) Dimethoxy 50 50 20 25 40 40 50 15compound Ratio (mol %)* Curing speed ⊚ Δ X X Δ Δ Δ X Resistance to A B CC B B B C weather Elongation (%) 320 250 130 180 230 270 120 130Breaking strength 3.2 2.5 2.0 2.4 2.3 1.9 2.1 2.0 (kg/cm³) *Mol % basedon the silicon-containing compound used when the copolymer rubber ororganic polymer is produced Evaluation of resistance to weather: A: Nocracks or molten portion observed; B: Small cracks or molten portionobserved, although slightly, C: Cracks or molten portion observed.

TABLE A4 (Effects of incorporation of the trimethoxy compound)COMPARATIVE EXAMPLES A16 A17 A18 A19 A20 A21 A22 A23 Copolymer PRODUC-REFERENCE REFERENCE REFERENCE REFERENCE REFERENCE REFERENCE REFERENCErubber or TION EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLEpolymer EXAMPLE A1 A2 A3 A4 A5 A6 A7 Trimethoxy 0.27 0.27 0.21 0.16 0.200.24 0.38 0.13 compound Quantity (g) Trimethoxy 50 50 20 25 40 40 50 15compound Ratio (mol %)* Curing speed ⊚ Δ X X Δ Δ Δ X Resistance to A B CC B B B C weather Elongation (%) 270 200 100 130 180 210 90 110 Breakingstrength 2.5 2.1 1.9 2.0 2.0 1.6 1.8 1.7 (kg/cm³) *Mol % based on thesilicon-containing compound used when the copolymer rubber or organicpolymer is produced Evaluation of resistance to weather: A: No cracks ormolten portion observed, B: Small cracks or molten portion observed,although slightly, C: Cracks or molten portion observed.

Examples A2 to A4

The cured sheet was prepared for each of EXAMPLES A2 to A4 and subjectedto the tensile test in the same manner as in EXAMPLE A1, except thateach silanol compound shown in Table A5 was incorporated in thesilyl-containing ethylene/propylene/5-vinyl-2-norbornene randomcopolymer rubber (A-1) prepared in PRODUCTION EXAMPLE in place oftriphenyl silanol. The results are given in Table A5.

As shown, each silanol compound achieved high elongation.

Comparative Examples A24 to A26

The cured sheet was prepared for each of COMPARATIVE EXAMPLES A24 to A26and subjected to the tensile test in the same manner as in COMPARATIVEEXAMPLE A1, except that each silanol compound shown in Table A5 wasincorporated in the organic polymer (1) prepared in REFERENCE EXAMPLE A1in place of triphenyl silanol. The results are given in Table A5.

As shown, each silanol compound achieved high elongation.

TABLE A5 COMPARATIVE EXAMPLES EXAMPLES A24 A25 A26 A2 A3 A4 REFERENCEREFERENCE REFERENCE Copolymer rubber or PRODUCTION PRODUCTION PRODUCTIONEXAMPLE EXAMPLE EXAMPLE polymer EXAMPLE EXAMPLE EXAMPLE A1 A1 A1 Silanolcompound MeSiOH EtSiOH Ph(Me)SiOH MeSiOH EtSioH Ph(Me)SiOH Type Quantity(g) 0.09 0.09 0.36 0.09 0.09 0.36 Ratio (mol %)* 30 20 50 30 20 50Curing speed ⊚ ⊚ ⊚ Δ Δ Δ Resistance to weather A A A B B B Elongation(%) 480 520 660 390 400 480 Breaking strength (kg/cm³) 2.9 3.1 2.6 2.42.5 2.0 *Mol % based on the silicon-containing compound used when thecopolymer rubber or organic polymer is produced Evaluation of resistanceto weather: A: No cracks or molten portion observed, B: Small cracks ormolten portion observed, although slightly, C: Cracks or molten portionobserved.

Examples A5 to A7

The cured sheet was prepared for each of EXAMPLES A5 to A7 and subjectedto the tensile test in the same manner as in EXAMPLE A1, except thateach silanol compound capable of forming a silanol-containing compoundby reacting with moisture, shown in Table A6, was incorporated in thesilyl-containing ethylene/propylene/5-vinyl-2-norbornene randomcopolymer rubber (A-1) prepared in PRODUCTION EXAMPLE in place oftriphenyl silanol. The results are given in Table A6.

As shown, incorporation of each of the compounds capable of forming asilanol-containing compound by reacting with moisture brings aboutalmost the same effect as that of the silanol compound, greatlyimproving elongation of the cured acrylic-based polymer which tends toshow insufficient elongation.

Comparative Examples A27 to A29

The cured sheet was prepared for each of COMPARATIVE EXAMPLES A27 to A29and subjected to the tensile test in the same manner as in COMPARATIVEEXAMPLE A1, except that each silicon compound capable of forming asilanol-containing compound by reacting with moisture, shown in TableA6, was incorporated in the organic polymer (1) prepared in REFERENCEEXAMPLE A1 in place of triphenyl silanol. The results are given in TableA6.

As shown, incorporation of each of the compounds capable of forming asilanol-containing compound by reacting with moisture brings aboutalmost the same effect as that of the silanol compound, greatlyimproving elongation of the cured acrylic-based polymer which tends toshow insufficient elongation.

TABLE A6 COMPARATIVE EXAMPLES EXAMPLES A27 A28 A29 A5 A6 A7 REFERENCEREFERENCE REFERENCE Copolymer rubber or PRODUCTION PRODUCTION PRODUCTIONEXAMPLE EXAMPLE EXAMPLE polymer EXAMPLE EXAMPLE EXAMPLE A1 A1 A1 Silanolcompound Si(1) Si(2) Si(3) Si(1) Si(2) Si(3) Type Quantity (g) 0.16 0.270.22 0.16 0.27 0.22 Ratio (mol %)* 30 40 50 30 40 50 Curing speed ⊚ ⊚ ⊚X Δ Δ Resistance to weather A A A C B B Elongation (%) 550 590 620 420480 480 Breaking Strength (kg/cm³) 2.9 2.5 2.6 2.4 2.2 2.2 *Mol % basedon the silicon-containing compound used when the copolymer rubber ororganic polymer is produced Si(1): Me₃SiNHSiMe₃ Si(2):Me₃SiO—C(CH₃)NSiMe₃ Si(3): CH₃—CO—NHSiMe₂ Evaluation of resistance toweather: A: No cracks or molten portion observed, B: Small cracks ormolten portion observed, although slightly, C: Cracks or molten portionobserved.

Examples B Series

The composition, iodine value, intrinsic viscosity [η] and molecularweight distribution (Mw/Mn) of the copolymer rubber used in each ofEXAMPLES and COMPARATIVE EXAMPLES were determined by the methoddescribed earlier.

The weather resistance test was conducted by the following method.

[Accelerated Weather Resistance Test]

The weather resistance test was conducted in accordance with JIS B-7753using a Sunshine Carbon Arc weatherometer.

<Testing Conditions>

-   Light irradiation/rainfall cycles: Irradiation for 120    minutes/rainfall for 18 minutes-   Black panel temperature: 63±2° C.-   Tank inside temperature: 40±2° C.-   Total light irradiation time: 1000 hours-   Analytical method:In accordance with JIS K-6301

Production Example B1

[Production of silyl-containing ethylene/propylene/5-vinyl-2-norborneneRandom Copolymer Rubber (A-1)]

The three-component copolymerization was effected continuously in astainless steel polymerization reactor having an essential capacity of100 L, equipped with agitator blades (agitating rotation speed: 250rpm), wherein hexane, ethylene, propylene and 5-vinyl-2-norbornene werecontinuously supplied at 60 L, 2.5 kg, 4.0 kg and 380 g per hour,respectively, from the reactor side into the liquid phase, and hydrogen,VO(OEt)₂Cl and Al (Et)_(1.5)Cl_(1.5) as the catalysts at 700 L, 45 mmolsand 315 mmols per hour, respectively, also continuously.

The copolymerization effected under the above conditions produced theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A₀-1)in a form of uniform solution.

A small quantity of methanol was added to the polymer solution,continuously withdrawn from the reactor bottom, to terminate thepolymerization. The polymer was separated from the solvent bysteam-stripping the solution, and dried at 55° C. for 48 hours under avacuum.

The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber(A₀-1) thus produced contained ethylene at 68% by mol, and had anintrinsic viscosity [η] of 0.2 dl/g measured in decalin kept at 135° C.,iodine value (IV) of 10(g/100 g) and Mw/Mn of 15.

Two % toluene solution (0.3 g) of chloroplatinic acid and 1.5 g ofmethyldimethoxysilane were added to 100 g of theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A₀-1),and they were allowed to react with each other at 120° C. for 2 hours.The excess methyldimethoxysilane and the solvent (toluene) weredistilled off from the effluent. This produced 101.5 g of theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1)containing dimethoxymethylsilyl group (—SiCH₃(OCH₃)₂).

Production Example B2

By a syringe, 54 mL of ethyl cyclohexane (left at least for a night anddried by molecular sieves 3A), 126 mL of toluene (left at least for anight and dried by molecular sieves 3A) and 1.16 g (5.02 mols) of p-DCC,represented by the following formula, were charged into a 500 mLpressure-resistant glass reactor equipped with a 3-way cock, purged bynitrogen.

Then, a liquefied gas collecting tube of pressure-resistant glass,equipped with a needle valve and containing 56 mL of isobutylenemonomer, was connected to the above-described 3-way cock. Thepolymerization reactor was cooled in a dry ice/ethanol bath kept at −70°C., and evacuated of the vapor phase to a vacuum by a vacuum pump. Then,the needle valve was opened, to charge the isobutylene monomer throughthe liquefied gas collecting tube into the polymerization reactor, andthe reactor was returned back to the normal pressure with nitrogen fromthe one port of the 3-way cock.

Next, 0.093 g (1.0 mmol) of 2-methyl pyridine was added to the reactionsystem, and then 1.65 mL (15.1 mmols) of titanium tetrachloride wasadded, to initiate the polymerization. Then, 1.22 g (10.8 mmols) ofallyl trimethylsilane was added 70 minutes after the reaction wasinitiated, to chemically introduce the allyl group into the polymer atthe terminal. The reaction solution, obtained 120 minutes after thereaction was initiated, was washed 4 times each with 200 mL of water,and the solvent was distilled off to produce the isobutylene-basedpolymer with the allyl group at the terminal.

Next, 40 g of the isobutylene-based polymer with the allyl group at theterminal was dissolved in 20 mL of n-heptane, and the mixture was heatedto around 70° C., to which 1.5 [eq/vinyl group] of methyldimethoxysilane and 1×10⁻⁴ [eq/vinyl group] of a platinum/vinyl siloxanecomplex were added, for the hydrosilylation. The reaction was followedby FT-IR. The olefin absorption at 1640 cm⁻¹ disappeared in around 4hours.

The reaction solution was concentrated under a vacuum, to produce theisobutylene polymer with the reactive silicon groups at both terminals,represented by the following formula:

The polymer yield was estimated from the quantity produced. It was alsoanalyzed for Mn and Mw/Mn by GPC, and for the terminal structure bycomparing the intensities of the ¹H-NMR-analyzed resonance signals ofproton relevant to each structure (proton derived from the initiator:6.5 to 7.5 ppm, methyl proton bonded to the silicon atom, derived fromthe polymer terminal: 0.0 to 0.1 ppm, methoxy proton: 3.4 to 3.5) witheach other.

The ¹H-NMR analysis was conducted at 300 MHz using a Varian Gemini 300(300 MHz for ¹H) in CDCl₃.

The FT-IR analysis was conducted by an analyzer (Shimadzu IR-408), andGPC analysis was conducted with a Waters LC Module 1 as the liquidsending system and Shodex K-804 as the column. The molecular weight wasestimated as relative to the polystyrene standard. The polymer thusprepared had an Mn of 11,400, Mw/Mn of 1.23 and Fn (silyl) of 1.76,wherein the number-average molecular weight was as polystyrene, andnumber of the terminal silyl functional group was that per 1 mol ofisobutylene polymer.

Production Example B3

The isobutylene-based polymer with the reactive silicon group wasprepared in the same manner as in PRODUCTION EXAMPLE B2, except thatdifferent quantities of p-DCC and allyl trimethylsilane were charged,2.32 g (10.0 mmols) and 14.4 g (126.0 mmols), respectively.

The polymer thus prepared had an Mn of 5,780, Mw/Mn of 1.28 and Fn(silyl) of 1.93.

Examples B1 and B2, and Comparative Examples B1 to B3

A mixture containing the silyl-containingethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1)produced in PRODUCTION EXAMPLE B1 was prepared. It was composed of 100parts by weight of the copolymer rubber (A-1), 90 parts (by weight) of aparaffin-based process oil (Idemitsu Kosan, Diana Process oil PS-32™),180 parts of limestone powder (Shiraishi Calcium, PO320B10™), 50 partsof colloidal calcium carbonate (Shiraishi K. K., EDS-D10A™), 100 partsof talc (Fuji Talc Kogyo, Talc LMR™), 3 parts of nickeldimethyldithiocarbamate as the light stabilizer (Sanshin ChemicalIndustry Co., Sandant NBC™), 5 parts of a dipping inhibitor (KusumotoKasei, Disparlon#305™),1 part of a hindered phenol-based antioxidant(Ciba-Geigy Japan, Irganox 1010™), 1 part of a salicylate-basedultraviolet ray absorber (Sumitomo Chemical, Sumisorb 400™), 1 part of ahindered amine-based light stabilizer (Sankyo, Sanol LS-765™), 3 partsof dipentaerythritol penta- and hexa-acrylate as the light-curablecompounds (TOAGOSEI, Aronix M-400™), 2 parts ofγ-glycidoxypropyltrimethoxysilane (Nippon Unicar, Silane Coupling AgentA-187), 4 parts of γ-isocyanatepropyltriethoxysilane (Nippon Unicar,Silane Coupling Agent A-1310) as the isocyanate-containing silanecoupling agent for the present invention, and the silicon compounddescribed below in parts given in Table B2, all parts by weight. Eachmixture was well kneaded by a3-paint roll unit, to produce the majoringredient.

Diphenyl dimethoxysilane (Shin-Etsu Chemical, LS-5300™), a silanol-freesilicon compound as the component B2 for the present invention wasincorporated in parts given in Table B1 for EXAMPLES B1 and B2, andCOMPARATIVE EXAMPLE B1. Diphenyl disilanol (Chisso Co., D₆₁₅₀™) as asilanol-containing silicon compound was incorporated in parts given inTable B1 for COMPARATIVE EXAMPLES B2 and B3.

The curing agent was prepared by the following procedure: a mixturecomprising 16 parts of a paraffin-based process oil (Idemltsu Kosan,Diana Process Oil PS-32™), 10parts of limestone powder (Maruo Calcium,Snowlite SS™), 2.5 parts of carbon black (Mitsubishi Chemical, CB#30™),2 parts of H₂O, and the silanol condensing catalyst described below inparts given in Table B1, all parts by weight, was manually kneaded in adisposal cup and stirred 3 times at 10,000 rpm each for 10 minutes by ahomogenizer (Nihon Seiki Sesakusho Co., Ltd., Excel Auto Homogenizer).

EXAMPLES B1 and B2, and COMPARATIVE EXAMPLE B2 and B3 incorporated 4parts by weight of dibutyl tin dimethoxide (Aldrich Chemical) as thecomponent C for the present invention, which was a tetravalent tincompound as the silanol condensing catalyst, whereas COMPARATIVE EXAMPLEB1 incorporated 4 parts by weight of tin octylate (NITTO KASEI, U-₂₈™)as a divalent tin compound.

Curability of each composition was evaluated, after the above-describedmajor ingredient and curing agent were kneaded, by following hardness ofthe cured product.

The test piece for measuring hardness comprised 16 parts of the majoringredient and 1 part of the curing catalyst, all by weight, wherein themixture was thoroughly kneaded and cured in a constant-temperature bathkept at 25° C. in a mold, 12 by 12 by 50 mm, lined with a Teflon sheet.Hardness of the rectangular parallelepiped test piece, cured at 25° C.,was measured using a hardness meter (Shimadzu, Hardness Meter 200) inaccordance with JIS K-6301/1975 for the spring type hardness test A.Curability was determined by measuring time required for the compositionto attain hardness of 20 immediately after kneading of the majoringredient and curing agent was completed. The results are given inTable B1.

TABLE B1 Time required to Silanol condensing Silicon compounds attainhardness of Resistance to Catalysts (Quantity) (Quantity) 20 (hrs)Weather EXAMPLE B1 (C₄H₉)₂Sn(OCH₃)₂ (C₆H₅)₂Si(OCH₃)₂ 1 No cracks ormolten (4 parts by weight) (0.5 part by weight) portion observed EXAMPLEB2 (C₄H₉)₂Sn(OCH₃)₂ (C₆H₅)₂Si(OCH₃)₂ 1 No cracks or molten (4 parts byweight) (1.0 part by weight) portion observed COMPARATIVE Sn(OCOC₇H₁₅)₂(C₆H₅)₂Si(OCH₃)₂ 3 No cracks or molten EXAMPLE B1 (4 parts by weight)(0.5 part by weight) portion observed COMPARATIVE (C₄H₉)₂Sn(OCH₃)₂(C₆H₅)₂Si(OH)₂ 2 No cracks or molten EXAMPLE B2 (4 parts by weight) (0.5part by weight) portion observed COMPARATIVE (C₄H₉)₂Sn(OCH₃)₂(C₆H₅)₂Si(OH)₂ 2 No cracks or molten EXAMPLE B3 (4 parts by weight) (1.0part by weight) portion observed

Reference Examples B1 to B6

The polymer prepared in PRODUCTION EXAMPLE B2 as the saturatedhydrocarbon-based polymer was incorporated with the followingcomponents, wherein the quantity of each component is represented aspart(s) by weight per 100 parts by weight of the polymer: 90 parts of aparaffin-based process oil (Idemitsu Kosan, Diana Process oil PS-32™),180 parts of limestone powder (Shiraishi Calcium, PO320B10™), 50 partsof colloidal calcium carbonate (Shiraishi K. K., EDS-D10A™), 100 partsof talc (Fuji Talc Kogyo, Talc LMR™), 3 parts of nickeldimethyldithiocarbamate as the light stabilizer (Sanshin Kagaku Kogyo,Sandant NBC™), 5 parts of a dipping inhibitor (Kusumoto Kasei, Disparlon#305™), 1 part of a hindered phenol-based antioxidant (Ciba-Geigy Japan,Irganox 1010™), 1 part of a salicylate-based ultraviolet ray absorber(Sumitomo Chemical, Sumisorb 400™), part of a hindered amine-based lightstabilizer (Sankyo, Sanol LS-765™), 3 parts of dipentaerythritol penta-and hexa-acrylate as the light-curable compounds (TOAGOSEI, AronixM-400™), 2 parts of γ-glycidoxypropyltrimethoxysilane (Nippon Unicar,Silane Coupling Agent A-187), 4 parts ofγ-isocyanatepropyltriethoxysilane (Nippon Unicar, Silane Coupling AgentA-1310) as the isocyanate-containing silane coupling agent for thepresent invention, and the silicon compound described below in partsgiven in Table B2. Each mixture was well kneaded by a 3-paint roll unit,to produce the major ingredient.

Diphenyl dimethoxysilane (Shin-Etsu Chemical, LS-5300™), a silanol-freesilicon compound as the component B2 for the present invention wasincorporated in parts given in Table B2 for REFERENCE EXAMPLES B1 to B3,no silicon compound was incorporated in REFERENCE EXAMPLE B4, anddiphenyl disilanol (Chisso, D6150™) as a silanol-containing siliconcompound was incorporated in parts given in Table B2 for REFERENCEEXAMPLES B5 and B6.

The curing agent was prepared by the following procedure: a mixturecomprising 16 parts of a paraffin-based process oil (Idemitsu Kosan,Diana Process Oil PS-32™), 10 parts of limestone powder (Maruo Calcium,Snowlite SS™) 2.5 parts of carbon black (Mitsubishi Chemical, CB#30™), 2parts of H₂O, and the silanol condensing catalyst described below inparts given in Table B2, all parts by weight, was manually kneaded in adisposal cup and stirred 3 times at 10,000 rpm each for 10 minutes by ahomogenizer (Nihon Seiki Sesakusho Co., Ltd., Excel Auto Homogenizer).

REFERENCE EXAMPLES B1 to B2 and B4 to B6 incorporated 4 parts by weightof dibutyl tin dimethoxide (Aldrich Chemical) as the component C for thepresent invention which was a tetravalent tin compound as the silanolcondensing catalyst, whereas REFERENCE EXAMPLE B3 incorporated 4 partsby weight of tin octylate (NITTO KASEI, U-28™) as a divalent tincompound.

Curability of each composition was evaluated, after the above-describedmajor ingredient and curing agent were kneaded, by following hardness ofthe cured product.

The test piece for measuring hardness comprised 16 parts of the majoringredient and 1 part of the curing catalyst, all by weight, wherein themixture was thoroughly kneaded and cured in a constant-temperature bathkept at 25° C. in a mold, 12 by 12 by 50 mm, lined with a Teflon sheet.Hardness of the rectangular parallelepiped test piece, cured at 25° C.,was measured using a hardness meter (Shimadzu, Hardness Meter 200) inaccordance with JIS K-6301/1975 for the spring type hardness test A.Curability was determined by measuring time required for the compositionto attain hardness of 20 immediately after kneading of the majoringredient and curing agent was completed. The results are given inTable B2.

TABLE B2 Time required to Silanol condensing Silicon compounds attainhardness of Resistance to catalysts (Quantity) (Quantity) 20 (hrs)Weather REFERENCE (C₄H₉)₂Sn(OCH₃)₂ (C₆H₅)₂Si(OCH₃)₂ 2.1 Molten portionEXAMPLE B1 (4 parts by weight) (0.5 part by weight) observed slightlyREFERENCE (C₄H₉)₂Sn(OCH₃)₂ (C₆H₅)₂Si(OCH₃)₂ 2.0 Molten portion EXAMPLEB2 (4 parts by weight) (1.0 part by weight) observed slightly REFERENCESn(OCOC₇H₁₅)₂ (C₆H₅)₂Si(OCH₃)₂ >12 Molten portion EXAMPLE B3 (4 parts byweight) (0.5 part by weight) observed slightly REFERENCE(C₄H₉)₂Sn(OCH₃)₂ Not used 4.0 Molten portion EXAMPLE B4 (4 parts byweight) (0 part by weight) observed slightly REFERENCE (C₄H₉)₂Sn(OCH₃)₂(C₆H₅)₂Si(OH)₂ 3.8 Molten portion EXAMPLE B5 (4 parts by weight) (0.5part by weight) observed slightly REFERENCE (C₄H₉)₂Sn(OCH₃)₂(C₆H₅)₂Si(OH)₂ 3.5 Molten portion EXAMPLE B6 (4 parts by weight) (1.0part by weight) observed slightly

Rererence Examples B7 to B9

The adhesion improving effect of the isocyanate-containing silanecoupling agent of the present invention was evaluated by the adhesiontest, described below.

The test piece for the tensile adhesion test was prepared in accordancewith the method specified by JIS A-5758/1992, wherein a glass substrateformed into an H-shape was filled with the composition (an accuratelyweighed 16:1 mixture of the major ingredient and curing agent preparedin REFERENCE EXAMPLE B1 for REFERENCE EXAMPLE B7, and of the majoringredient and curing agent prepared in REFERENCE EXAMPLE B2 forREFERENCE EXAMPLE B8) while breaking the bubbles in each composition byusing a spatula. Each composition was cured in an oven under theconditions of 23° C.×7 days+50° C.×7 days. The substrate used for the Htype tensile test was of aluminum (Taiyu Kizai, A1100P, 3 by 5 by 0.2 cmin size), in accordance with JIS H-4000. It was washed withmethylethylketone (Wako-Junyaku Kogyo special grade) and wiped withclean cotton cloth, before it was filled with the composition. It wasnot coated with a primer.

The adhesion test was conducted in REFERENCE EXAMPLE B9 in the samemanner as in REFERENCE EXAMPLE B7, except thatγ-isocyanatepropyltriethoxysilane was not used.

The test piece prepared above for the H type tensile test was tested fortensile adhesion, after it was cured, to evaluate adhesion in theabsence of a primer by comparing the tensile characteristics withfractured morphology.

The tensile adhesion test was conducted in accordance with JISA-5758/1992 in a constant-temperature chamber kept at 23° C. and RH(relative humidity) 50±10% at a tensile speed of 50 mm/minute using aShimadzu's Autograph AG-2000A.

The results are given in Table B3.

Examples B3 to B5

The adhesion test was conducted in EXAMPLES B3 to B5 in the same manneras in REFERENCE EXAMPLES B7 to B9, except that the polymer prepared inPRODUCTION EXAMPLE B2 was replaced by the silyl-containingethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1)prepared in PRODUCTION EXAMPLE B1.

The results are given in Table B4.

TABLE B3 Isocyanate-containing silane Silanol condensing SiliconCompounds coupling agent Adhesion tests Resistance to Catalysts(Quantity) (Quantity) (Quantity) Fractured morphology Weather REFERENCE(C₄H₉)₂Sn(OCH₃)₂ (C₆H₅)₂Si(OCH₃)₂ OCNC₃H₆Si(OCH₃)₃ Cohesive fractureMolten portion EXAMPLE B7 (4 parts by weight) (0.5 part by weight) (4parts by weight) observed slightly REFERENCE (C₄H₉)₂Sn(OCH₃)₂(C₆H₅)₂Si(OCH₃)₂ OCNC₃H₆Si(OCH₃)₃ Cohesive fracture Molten portionEXAMPLE B8 (4 parts by weight) (1.0 part by weight) (4 parts by weight)observed slightly REFERENCE (C₄H₉)₂Sn(OCH₃)₂ (C₆H₅)₂Si(OCH₃)₂ Not usedInterfacial fracture Molten portion EXAMPLE B9 (4 parts by weight) (0.5part by weight) (0 part by weight) observed slightly

TABLE B4 Isocyanate-containing Silanol condensing Silicon Compoundssilane coupling agent Adhesion tests Resistance to Catalysts (Quantity)(Quantity) (Quantity) Fractured morphology Weather EXAMPLE B3(C₄H₉)₂Sn(OCH₃)₂ (C₆H₅)₂Si(OCH₃)₂ OCNC₃H₆Si(OCH₃)₃ Cohesive fracture Nocracks or molten (4 parts by weight) (0.5 part by weight) (4 parts byweight) portion observed EXAMPLE B4 (C₄H₉)₂Sn(OCH₃)₂ (C₆H₅)₂Si(OCH₃)₂OCNC₃H₆Si(OCH₃)₃ Cohesive fracture No cracks or molten (4 parts byweight) (1.0 part by weight) (4 parts by weight) portion observedEXAMPLE B5 (C₄H₉)₂Sn(OCH₃)₂ (C₆H₅)₂Si(OCH₃)₂ Not used Interfacialfracture No cracks or molten (4 parts by weight) (0.5 part by weight) (0part by weight) portion observed

The weather resistance tests were conducted according to the methoddescribed above for the cured products prepared in EXAMPLES B1 to B5,COMPARATIVE EXAMPLES B1 to B3 and REFERENCE EXAMPLES B1 to B9. Theresults are given in Tables B1 to B4.

Examples C Series

The composition, iodine value, intrinsic viscosity [η] and molecularweight distribution (Mw/Mn) of the copolymer rubber used in each ofEXAMPLES and COMPARATIVE EXAMPLES were determined by the methodsdescribed earlier.

Production Example

[Production of ethylene/propylene/5-vinyl-2-norbornene random copolymerrubber (A-1)]

The three-component copolymerization was effected continuously in astainless steel polymerization reactor having an essential capacity of100 L, equipped with agitator blades (agitating rotation speed: 250rpm), wherein hexane, ethylene, propylene and 5-vinyl-2-norbornene werecontinuously supplied at 60 L, 2.5 kg, 4.0 kg and 380 g per hour,respectively, from the reactor side into the liquid phase, and hydrogen,VO(OEt)₂Cl and Al(Et)_(1.5)Cl_(1.5) as the catalysts at 700 L, 45 mmolsand 315 mmols per hour, respectively, also continuously.

The copolymerization effected under the above conditions produced theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A₀-1)in a form of uniform solution.

A small quantity of methanol was added to the polymer solution,continuously withdrawn from the reactor bottom, to terminate thepolymerization. The polymer was separated from the solvent bysteam-stripping the solution, and dried at 55° C. for 48 hours under avacuum.

The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber(A₀-1) thus produced contained ethylene at 68% by mol, and had anintrinsic viscosity [η] of 0.2 dl/g measured in decalin kept at 135° C.,iodine value (IV) of 10(g/100 g) and Mw/Mn of 15.

Two % toluene solution (0.3 part by weight) of chloroplatinic acid, andmethyldimethoxysilane, 1.5 parts by weight were added to 100 parts byweight of the ethylene/propylene/5-vinyl-2-norbornene random copolymerrubber (A₀-1), and they were allowed to react with each other at 120° C.for 2 hours. The excess methyldimethoxysilane and the solvent (toluene)were distilled off from the effluent. This produced 101.5 parts byweight of the ethylene/propylene/5-vinyl-2-norbornene random copolymerrubber (A-1) containing dimethoxymethylsilyl group (—Si(CH₃)(OCH₃)₂)

Example C1

A mixture containing the ethylene/propylene/5-vinyl-2-norbornene randomcopolymer rubber (A-1) containing the hydrolyzable silyl group, preparedin the above-described PRODUCTION EXAMPLE, was stirred at 120° C. for 2hours under a vacuum in a kneader (planetary mixer), which could beclosed, and dehydrated. The mixture was composed of 100 parts of thecopolymer rubber (A-1), 55 parts of diisodecyl phthalate (DIDP) as theplasticizer, 120 parts of surface-treated colloidal calcium carbonate asthe filler, 20 parts of titanium oxide, 2 parts of aliphatic amide waxas the dipping inhibitor, 1 part of an ultraviolet ray absorber, and 1part of a light stabilizer, all part(s) by weight. The mixture wascooled to room temperature, and incorporated with 2 parts of vinyltrimethoxysilane as the viscosity stabilizer, 2 parts of a curingcatalyst (NITTO KASEI, U-220) and 3 parts ofN-(β-aminoethyl)-γ-aminopropyltrimethylsiloxydimethoxysilane as thesurface modifier, all part(s) by weight. The resultant mixture wasstirred at room temperature, and put in a closed container, to produce aone-liquid type curable composition. Each composition prepared inEXAMPLES C1 to C3 was evaluated by the following methods immediatelyafter it was prepared. The one stored at 50° C. for 14 days wasevaluated as well.

Each composition was spread to a thickness of 3 mm, cured at 23° C. andRH 55%, and, after 1 day, painted with a total of 5 types of commercialsolvent-based acrylic paints for industrial purposes (3 types ofacrylourethane-based ones, 1 type of acrylic lacquer, and 1 type ofacryloenamel) with a brush. It was then tested, after 7 days, by achecker pattern with 25 meshes (2 mm square) using a cellophane tape(Nichiban), wherein the composition was evaluated by percentage of themeshes remaining on the sealant surface, based on the total meshes.

The residual tackiness was evaluated for each composition spread to athickness of 3 mm, and cured at 23° C. and RH 55% for 1 and 7 days, bythe touch of finger on the cured surface. Each composition was alsoevaluated for its tensile characteristics in accordance with JIS K-6251.The results are given in Table C1.

Each composition was further tested for its curing speed and weatherresistance by the following methods. The results are given in Table C1.

(1) Curing Speed Test

Each composition was spread to a thickness of 3 mm, and cured at 23° C.and RH 55%, to measure its curing speed, where curing speed was definedas time required for the composition to attain hardness of 20 (JIS A).

(2) Weather Resistance Test (Ozone-caused Aging Test)

The accelerated weather resistance test was conducted in accordance withJIS B-7753 under the following conditions:

-   Analyzer:Sunshine Carbon Arc Weatherometer-   Light irradiation/rainfall cycles:Irradiation for 120    minutes/rainfall for 18 minutes-   Black panel temperature: 63±2° C.-   Tank inside temperature: 40±2° C.-   Total light irradiation time: 1000 hours

Examples C2 and C3

The composition for each of EXAMPLES C2 and C3 was prepared in the samemanner as in EXAMPLE C1, except that the content ofN-(β-aminoethyl)-γ-aminopropyltrimethylsiloxydimethoxysilane was changedto a level given in Table C1, and incorporated withN-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (A-1120) as the commontackifier. It was tested in the same manner. The results are given inTable C1.

Comparative Examples C1 and C2

The composition for each of COMPARATIVE EXAMPLES C1 and C2 was preparedin the same manner as in EXAMPLE C1, except thatN-(β-aminoethyl)-γ-aminopropyltrimethylsiloxydimethoxysilane wasreplaced by N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (A-1120) asthe common tackifier. It was tested in the same manner. The results aregiven in Table C1.

As shown in Table C1, each of the composition of the present inventionis excellent in residual tackiness on the cured surface and adhesion tothe paint. It also shows that the composition has adhesion varying as itis stored, a phenomenon which is not substantiated yet.

Rererence Example C1

A mixture containing the propylene oxide polymer having 2.1methyldimethoxysilyl groups [—Si(CH₃)(OCH₃)₂] on the average in themolecule and a number-average molecular weight of 17,000 was stirred at120° C. for 2 hours under a vacuum in a kneader (planetary mixer), whichcould be closed, and dehydrated. The mixture was composed of 100 partsof the above polymer, 55 parts of diisodecyl phthalate (DIDP) as theplasticizer, 120 parts of surface-treated colloidal calcium carbonate asthe filler, 20 parts of titanium oxide, 2 parts of aliphatic amide waxas the dipping inhibitor, 1 part of an ultraviolet ray absorber, and 1part of a light stabilizer, all part(s) by weight. The mixture wascooled to room temperature, and incorporated with 2 parts of vinyltrimethoxysilane as the viscosity stabilizer, 2 parts of a curingcatalyst (NITTO KASEI, U-220) and 3 parts ofN-(β-aminoethyl)-γ-aminopropyltrimethylsiloxydimethoxysilane as thesurface modifier, all part(s) by weight. The resultant mixture wasstirred at room temperature, and put in a closed container, to produce aone-liquid type curable composition.

The above composition was tested in the same manner as in EXAMPLE C1.The results are given in Table C1.

TABLE C1 EXAMPLES COMPARATIVE EXAMPLES C1 C2 C3 C1 C2 C3 AdditiveN-(β-aminoethyl)-γ 3 3 4 3 -aminopropyltrimethyl- siloxydimethoxysilaneA-1120 1 1 3 5 Paint Initial (%) 85 100 100 5 5 90 adhesion Afterstorage (%) 65 90 85 40 50 70 Residual After one day ⊚ ⊚ ⊚ ◯ ◯ ⊚Tackiness* After seven days ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ Stress at 100% 1.0 1.1 1.0 0.90.9 1.0 elongation (MPa) Breaking strength 3.0 3.2 2.9 2.5 2.2 2.5 (MPa)Breaking elongation 550 500 580 490 450 450 (%) Time required to attain3.0 2.5 2.5 6.0 7.0 3.0 hardness of 20 (hrs) Resistance to weather Nocracks or No cracks or No cracks or No cracks or No cracks or Cracks ormolten portion molten portion molten portion molten portion moltenportion molten portion observed observed observed observed observedobserved *⊚: No residual tackiness observed, ◯: Residual tackinessobserved very slightly, Δ: Residual tackiness observed slightly; X:Sticky surface

Examples C4 to C8

A mixture containing the ethylene/propylene/5-vinyl-2-norbornene randomcopolymer rubber (A-1) containing the hydrolyzable silyl group, preparedin the above-described PRODUCTION EXAMPLE, was prepared for each ofEXAMPLES C4 to C8. The mixture was composed of 100 parts of thecopolymer rubber (A-1), 55 parts of diisodecyl phthalate (DIDP) as theplasticizer, 120 parts of surface-treated colloidal calcium carbonate asthe filler, 20 parts of titanium oxide, 2 parts of aliphatic amide waxas the dipping inhibitor, 1 part of an ultraviolet ray absorber, 1 partof a light stabilizer, 2 parts of vinyl trimethoxysilane as theviscosity stabilizer, 2 parts of a curing catalyst (NITTO KASEI, U-220),and a silicon compound having at least one amino group and at least onetrialkylsiloxy group in the molecule, shown in Table C2, as the surfacemodifier all part(s) by weight. Each composition was only stirred atroom temperature; unlike the ones prepared in EXAMPLES C1 to C3, whichwere dehydrated under a vacuum and put in a closed container.

Each composition was spread to a thickness of 3 mm, cured at 23° C. andRH 55%, and, after 1 day, painted with a total of 5 types of commercialsolvent-based paints for industrial purposes with a brush. It was thentested, after 7 days, by a checker pattern with 25 meshes (2 mm square)using a cellophane tape (Nichiban), wherein the composition wasevaluated by percentage of the meshes remaining on the sealant surface,based on the total meshes. The results are given in Table C2.

Each composition was further tested for its residual tackiness, tensileproperty, curing seed and weather resistance. The results are also givenin Table C2.

Comparative Examples C3 and C4

COMPARATIVE EXAMPLES C3 and C4 were conducted in the same manner as inEXAMPLE C4, except thatN-(β-aminoethyl)-γ-aminopropyltrimethylsiloxydimethoxysilane was notused (COMPARATIVE EXAMPLE C4), or 3 parts by weight ofN-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (A-1120) was used inplace of N-(β-aminoethyl)-γ-aminopropyltrimethylsiloxydimethoxysilane(COMPARATIVE EXAMPLE C3). The results are also given in Table C2.

TABLE C2 COMPARATIVE COMPARATIVE EXAMPLE C4 EXAMPLE C5 EXAMPLE C6EXAMPLE C7 EXAMPLE C8 EXAMPLE C3 EXAMPLE C4 Additive N-(β-aminoethyl)-γ-3 2.5 1.5 aminopropyltrimethyl- siloxydimethoxysilaneγ-aminopropyltrimethyl- 3 siloxydimethoxysilane N,N-dimethyl-γ- 3aminoproyltrimethyl- dimethoxysilane A-1120 3 3 3 Paint Adhesion (%) 9885 100 86 80 0 0 Residual tackiness After one day ⊚ ⊚ ⊚ ⊚ ⊚ ◯ Δ Aftertwo days ⊚ ⊚ ⊚ ⊚ ⊚ ◯ ◯ Stress at 100% elongation 0.70 0.55 0.30 0.800.75 0.70 0.40 (MPa) Breaking strength (MPa) 3.10 2.50 1.40 3.50 3.202.20 1.40 Breaking elongation (%) 630 750 950 560 590 430 570 Timerequired to attain 2.5 3.0 3.5 3.0 3.0 6.0 7.0 hardness of 20 (hrs)Resistance to weather No cracks or No cracks or No cracks or No cracksor No cracks or No cracks or No cracks or molten portion molten portionmolten portion molten portion molten portion molten portion moltenportion observed observed observed observed observed observed observed

Example C9 and Comparative Example C5

A mixture containing the ethylene/propylene/5-vinyl-2-norbornene randomcopolymer rubber (A-1) containing the hydrolyzable silyl group, preparedin the above-described PRODUCTION EXAMPLE, was prepared for each ofEXAMPLE C9 and COMPARATIVE EXAMPLE C5. The mixture was composed of 100parts by weight of the copolymer rubber (A-1), 2 parts by weight of acuring catalyst (NITTO KASEI, U-220), andN-(β-aminoethyl)-γ-aminopropyltrimethylsiloxydimethoxysilane (forEXAMPLE C9) or N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (A-1120)for COMPARATIVE EXAMPLE C5as the surface modifier. Each composition wasstirred at room temperature. It was spread to a thickness of 3 mm, curedat 23° C. and RH 55%, and, after 1 day, painted with a total of 5 typesof commercial solvent-based paints for industrial purposes with a brush.It was then tested, after 7 days, by a checker pattern with 25 meshes (2mm square) using a cellophane tape (Nichiban), wherein the compositionwas evaluated by percentage of the meshes remaining on the sealantsurface, based on the total meshes. The results are given in Table C3.

Each composition was further tested for its residual tackiness, tensileproperty, curing seed and weather resistance, as was the case with theone for EXAMPLE C1. The results are also given in Table C3.

TABLE C3 EXAMPLE COMPARATIVE C9 EXAMPLE C5 Additive N-(β-aminoethyl)- 3γ-aminopropyltrimethyl siloxydimethoxy- silane A-1120 3 Paint 90 0adhesion (%) Residual After one day ⊚ Δ tackiness After two days ⊚ ◯Tensile stress at 100% 0.40 0.50 elongation (MPa) Breaking strength(MPa) 0.52 0.58 Breaking elongation (%) 220 150 Time required to attain2.5 4 hardness of 20 (hrs) Resistance to weather No cracks Cracksobserved observed

Examples D Series

The composition, iodine value, intrinsic viscosity [η] and molecularweight distribution (Mw/Mn) of the copolymer rubber used in each ofEXAMPLES and COMPARATIVE EXAMPLES were determined by the methodsdescribed earlier.

Production Example

[Production of silyl-containing ethylene/propylene/5-vinyl-2-norbornenerandom Copolymer Rubber (A-1)]

The three-component copolymerization was effected continuously in astainless steel polymerization reactor having an essential capacity of100 L, equipped with agitator blades (agitating rotation speed: 250rpm), wherein hexane, ethylene, propylene and 5-vinyl-2-norbornene werecontinuously supplied at 60 L, 2.5 kg, 4.0 kg and 380 g per hour,respectively, from the reactor side into the liquid phase, and hydrogen,VO(OEt)₂Cl and Al(Et)_(1.5)Cl_(1.5) as the catalysts at 700 L, 45 mmolsand 315 mmols per hour, respectively, also continuously.

The copolymerization effected under the above conditions produced theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A₀-1)in a form of uniform solution.

A small quantity of methanol was added to the polymer solution,continuously withdrawn from the reactor bottom, to terminate thepolymerization. The polymer was separated from the solvent bysteam-stripping the solution, and dried at 55° C. for 48 hours under avacuum.

The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber(A₀-1) thus produced contained ethylene at 68% by mol, and had anintrinsic viscosity [η] of 0.2 dl/g measured in decalin kept at 135° C.,iodine value (IV) of 10(g/100 g) and Mw/Mn of 15.

Two % toluene solution (0.3 part by weight) of chloroplatinic acid andmethyldimethoxysilane, 1.5 parts by weight were added to 100 parts byweight of the ethylene/propylene/5-vinyl-2-norbornene random copolymerrubber (A₀-1), and they were allowed to react with each other at 120° C.for 2 hours. The excess methyldimethoxysilane and the solvent (toluene)were distilled off from the effluent. This produced 101.5 parts byweight of the ethylene/propylene/5-vinyl-2-norbornene random copolymerrubber (A-1) containing dimethoxymethylsilyl group (—Si(CH₃)(OCH₃)₂).

Example 1

The copolymer rubber (A-1), 100 g, prepared in the above-describedPRODUCTION EXAMPLE, was incorporated with 1.75 g of (CH₃)₃SiOC₆H₅, andthe resultant mixture was stirred at 80° C. for 2 hours. It was thenincorporated with 150 g of colloidal calcium carbonate treated with afatty acid (Shiraishi K. K., CCR™), 65 g of dioctyl phthalate, 1 g of ahindered phenol-based aging inhibitor (Ouchishinko Chemical IndustrialCo., Nocrac NS-6™), 3 g of tin octylate and 1 g of lauryl amine, and theresultant mixture was sufficiently kneaded using a 3-paint roll unit.

The composition thus prepared was used to form an H-2 type test piece inaccordance with JISA-5758 (base: anodized aluminum oxide, primer: NipponUnicar's APZ-730), which was cured under given conditions, and tested bya tensile tester to measure its H-type tensile properties. It was alsotested for tackiness by the touch of finger. Its storage stability wasevaluated by viscosity (B type viscosity at 23° C., poise) ratio, i.e.,ratio of viscosity of the composition stored at 50° C. for a week tothat of the one immediately after it was prepared. The results are givenin Table D1.

Each composition was further tested for its curing speed and weatherresistance by the following methods. The results are also given in TableD1.

(1) Curing Speed Test

The curable composition was cured under the conditions of 23° C. and 50%RH for 24 hours in a mold, 20 by 80 by 5 mm in size.

Next, the cured product was released from the mold, and thickness of thecured portion was measured by a dial gauge of weak spring force to 0.1mm, to evaluate its curing speed. It was marked with ◯ when itsthickness was 1 mm or more and x when it was less than 1 mm.

(2) Weather Resistance Test

The weather resistance test was conducted in accordance with JIS B-7753under the following conditions:

-   Analyzer: Sunshine Carbon Arc Weatherometer-   Light irradiation/rainfall cycles: Irradiation for 120    minutes/rainfall for 18 minutes-   Black panel temperature: 63±2° C.-   Tank inside temperature: 40±2° C.-   Total light irradiation time: 250 hours

Weather resistance was evaluated by visual observation of the surfaceaging (cracks and molten portion). The composition was marked with ◯when no crackings or molten portions were observed, and x when thesurface aging was observed.

The results are given in Table D1, wherein M₁₅₀ is the modulus when thetest piece is stretched by 150%, T_(B) is breaking modulus, E_(B) isbreaking elongation, and tackiness evaluation “A” means tackinesscomparable with that of the composition free of an organosiliconcompound (COMPARATIVE EXAMPLE D1) and “B” is tackiness more than theabove. For storage stability, the lower value means better storagestability.

Comparative Examples D1 to D3

The composition was prepared in COMPARATIVE EXAMPLE D1 in the samemanner as in EXAMPLE D1, except that C₆H₅OSi(CH₃)₃ was not used, andtested in the same manner. The results are given in Table D1.

The composition was prepared in each of COMPARATIVE EXAMPLES D2 and D3in the same manner as in EXAMPLE D1, except that C₆H₅OSi (CH₃)₃ wasreplaced by the same quantity of (CH₃)₃SiOH or (C₆H₅)₃SiOH,respectively, and tested in the same manner. The results are also givenin Table D1.

TABLE D1 Characteristics H type tensile properties Organosilicon M₁₅₀T_(B) E_(B) Tackiness Storage Curing Resistance to compounds (kg/cm²)(kg/cm²) (kg/cm²) (to the touch) stability speed weather EXAMPLE D1(CH₃)₃SiOC₆H₅ 2.6 6.0 720 A 1.01 ◯ ◯ COMPARATIVE Not used 5.3 7.7 320 A1.25 ◯ ◯ EXAMPLE D1 COMPARATIVE (CH₃)₃SiOH 3.0 6.1 460 A 0.97 ◯ ◯EXAMPLE D2 COMPARATIVE (C₆H₅)₃SiOH 2.5 5.8 690 B 0.97 ◯ ◯ EXAMPLE D3

The results given in Table D1 indicate that the composition with(CH₃)₃SiOH is lower in improvement extent of modulus and elongation,although excellent in tackiness, and that the composition with(C₆H₅)₃SiOH is deteriorated in tackiness, although improved in modulusand elongation. On the other hand, the composition with (CH₃)₃SiOC₆H₅ isimproved in modulus and elongation, and, at the same time, excellent intackiness.

Examples D2 to D5, and Comparative Examples D4 to D6

The composition was prepared in each of the above examples in the samemanner as in EXAMPLE D1, except that C₆H₅OSi(CH₃)₃ was replaced by theorganosilicon compound shown in Table D2, and tested in the same manner.The results are given in Table D2, together with those of thecomposition prepared in EXAMPLE D1.

TABLE D2 Characteristics Organosilicon M₁₅₀ Tackiness Storage CuringResistance to Compounds (kg/cm²) (to the touch) stability speed WeatherEXAMPLE D1 (CH₃)₃SiOC₆H₅ 2.6 A 1.01 ◯ ◯ EXAMPLE D2 (CH₃)₃SiOCH₃Cl 2.7 A1.02 ◯ ◯ EXAMPLE D3 ((CH₃)₃SiOCH₂)₂ 2.6 A 0.97 ◯ ◯ EXAMPLE D4

2.8 A 1.16 ◯ ◯ EXAMPLE D5 ((CH₃)₃SiO)₃B 2.7 A 0.99 ◯ ◯ COMPARATIVE((CH₃)₃Si)₂NH 2.7 A 1.36 ◯ ◯ EXAMPLE D4 COMPARATIVE ((CH₃)₃Si)₂NCH₃ 2.6A 1.86 ◯ ◯ EXAMPLE D5 COMPARATIVE (CH₃SiNH)₂CO 2.5 A 1.62 ◯ ◯ EXAMPLE D6

The results given in Table D2 indicate that each composition of thepresent invention is excellent in all of curing speed, modulus,tackiness, storage stability and resistance to weather, and that use ofthe organosilicon compound, which generates the compound working as thesilanol condensing catalyst, e.g., ammonia or amine, deterioratesstorage stability.

Reference Example D1

The composition was prepared in the same manner as in EXAMPLE D1, exceptthat 100 g of the copolymer rubber (A-1) was replaced by the propyleneoxide polymer having, in the molecule, 3 dimethoxysilyl groups on theaverage, represented by the following formula, and having an averagemolecular weight of 9,600, and tested in the same manner. The resultsare given in Table D4.

Reference Examples D2 to D4

The composition was prepared in REFERENCE EXAMPLE D2 in the same manneras in EXAMPLE D1, except that C₆H₅OSi(CH₃)₃ was not used, and tested inthe same manner. The results are given in Table D3.

The composition was prepared in each of REFERENCE EXAMPLES D3 and D4 inthe same manner as in EXAMPLE D1, except that C₆H₅OSi (CH₃)₃ wasreplaced by the same quantity of (CH₃)₃SiOH or (C₆H₅)₃SiOH,respectively, and tested in the same manner. The results are also givenin Table D3.

TABLE D3 Characteristics H type tensile properties Organosilicon M₁₅₀T_(B) E_(B) Tackiness Storage Curing Resistance to compounds (kg/cm²)(kg/cm²) (kg/cm²) (to the touch) stability speed Weather REFERENCE(CH₃)₃SiOC₆H₅ 2.5 5.8 710 A 0.92 ◯ X EXAMPLE D1 REFERENCE Not used 5.27.6 340 A 1.22 ◯ X EXAMPLE D2 REFERENCE (CH₃)₃SiOH 3.5 6.3 490 A 0.92 ◯X EXAMPLE D3 REFERENCE (C₆H₅)₃SiOH 2.5 5.9 680 B 0.92 ◯ X EXAMPLE D4

Reference Example D5 to D11

The composition was prepared in each of the above examples in the samemanner as in REFERENCE EXAMPLE D1, except that C₆H₅OSi(CH₃)₃ wasreplaced by the organosilicon compound shown in Table D4, and tested inthe same manner. The results are given in Table D4, together with thoseof the composition prepared in REFERENCE EXAMPLE D1.

TABLE D4 Characteristics Organosilicon M₁₅₀ Tackiness Storage CuringResistance to Compounds (kg/cm²) (to the touch) stability speed WeatherREFERENCE (CH₃)₃SiOC₆H₅ 2.5 A 0.92 ◯ X EXAMPLE D1 REFERENCE(CH₃)₃SiOCH₃Cl 3.3 A 1.02 ◯ X EXAMPLE D5 REFERENCE ((CH₃)₃SiOCH₂)₂ 2.2 A0.92 ◯ X EXAMPLE D6 REFERENCEEXAMPLE D7

3.3 A 1.18 ◯ X REFERENCE ((CH₃)₃SiO)₃B 3.1 A 0.92 ◯ X EXAMPLE D8REFERENCE ((CH₃)₃Si)₂NH 2.7 A 1.38 ◯ X EXAMPLE D9 REFERENCE((CH₃)₃Si)₂NCH₃ 3.6 A 1.78 ◯ X EXAMPLE D10 REFERENCE (CH₃SiNH)₂CO 4.3 A1.51 ◯ X EXAMPLE D11

Example E Series

The composition, iodine value, intrinsic viscosity [η] and molecularweight distribution (Mw/Mn) of the copolymer rubber used in each ofEXAMPLES and COMPARATIVE EXAMPLES were determined by the methodsdescribed earlier.

Each composition was tested for its curing speed and accelerated weatherresistance by the following methods.

(1) Curing Speed Tests

(1A)

Each curing composition was followed for changed frequency by a scanningVNC (SVNC, RAPRA TECHNOLOGY LTD.). Frequency increased with time andbecame stabilized, and curing speed was based on time required forfrequency to change by 95%, wherein the stabilized frequency was set at100%. The test was conducted at room temperature, in accordance with theinstructions described in the following manuals:

-   (i) Operating manual for the RAPRA's scanning, vibrating probe-type    curing tester (scanning VNC) (Software Version 2.2)-   (ii) Understanding the RAPRA's scanning, vibrating probe-type curing    tester (scanning VNC)(RTL/2844)    (1B)

The curable composition (stock material) was cured under the conditionsof 23° C. and 50% RH for 24 hours in a mold, 20 by 80 by 5 mm in size.

Next, the cured product was released from the mold, and thickness of thecured portion was measured by a dial gauge of weak spring force to 0.1mm, to evaluate its curing speed. It was marked with ◯ when itsthickness was 1 mm or more and x when it was less than 1 mm.

(2) Accelerated Weather Resistance Test

The weather resistance test was conducted in accordance with JIS B-7753under the following conditions, using a Sunshine Carbon Arcweatherometer:

<Test Conditions>

-   Light Irradiation/Rainfall Cycles: Irradiation for 120    minutes/rainfall for 18 minutes-   Black panel temperature: 63±2° C.-   Tank inside temperature: 40±2° C.-   Total light irradiation time: 500 hours

Production Example E1

[Production of silyl-containing ethylene/propylene/5-vinyl-2-norborneneRandom Copolymer Rubber (A-1)]

The three-component copolymerization was effected continuously in astainless steel polymerization reactor having an essential capacity of100 L, equipped with agitator blades (agitating rotation speed: 250rpm), wherein hexane, ethylene, propylene and 5-vinyl-2-norbornene werecontinuously supplied at 60 L, 2.5 kg, 4.0 kg and 380 g per hour,respectively, from the reactor side into the liquid phase, and hydrogen,VO(OEt)₂Cl and Al(Et)_(1.5)Cl_(1.5) as the catalysts at 700 L, 45 mmolsand 315 mmols per hour, respectively, also continuously.

The copolymerization effected under the above conditions produced theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A₀-1)in a form of uniform solution.

A small quantity of methanol was added to the polymer solution,continuously withdrawn from the reactor bottom, to terminate thepolymerization. The polymer was separated from the solvent bysteam-stripping the solution, and dried at 55° C. for 48 hours under avacuum.

The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber(A₀-1) thus produced contained ethylene at 68% by mol, and had anintrinsic viscosity [η] of 0.2 dl/g measured in decalin kept at 135° C.,iodine value (IV) of 10(g/100 g) and Mw/Mn of 15.

Two % toluene solution (0.3 g) of chloroplatinic acid and 1.5 g ofmethyldimethoxysilane were added to 100 g of theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A₀-1),and they were allowed to react with each other at 120° C. for 2 hours.The excess methyldimethoxysilane and the solvent (toluene) weredistilled off from the effluent. This produced 101.5 g of theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1)containing dimethoxymethylsilyl group (—SiCH₃(OCH₃)₂).

Production Example E2

[Production of silyl-containing Vinyl Polymer]

Xylene, 340 g was charged in a reactor, equipped with an agitator, athermometer, a nitrogen-supplying nozzle, a drip-feed funnel and acondenser, and heated at 110° C.

Then, the reactor was continuously charged for 3 hours with a solutionof 140 g of styrene, 166 g of butyl acrylate, 467 g of methylmethacrylate, 100 g of stearyl methacrylate, 117 g ofγ-methacryloxypropyltrimethoxysilane, 10 g of N-methylol acrylamide, 30g of γ-mercaptopropyltrimethoxysilane and 30 g ofazobisisobutylonitrile.

On completion of the addition of the monomer, a separately preparedsolution of 3 g of azobisisobutylonitrile dissolved in 200 g of toluenewas added to the above mixture in 1 hour for the polymerization foranother 1 hour, to produce the silyl-containing vinyl resin.

The silyl-containing vinyl resin solution thus prepared containednonvolatiles at 65%. The resin had a number-average molecular weight of4,400, determined by GPC.

Production Example E3

[Production of Product of the Reaction Between an Epoxy Compound and anAcidic Phosphate Ester]

Monobutyl phosphate, 50 g (Daihachi Kagaku, MP-4) having an acid valueof 670 was charged in a reactor, equipped with an agitator, athermometer, a nitrogen-supplying nozzle, a drip-feed funnel and acondenser, to which 70.5 g of γ-glycidoxypropyltrimethoxysilane wasadded slowly dropwise in a nitrogen atmosphere, with stirring. Afterheat generation was no longer observed, the mixture was further heatedat 80° C. for 1 hour, to continue the reaction. The effluent wasincorporated with 12 g of methyl orthoacetate, 12 g of methanol and 96.5g of xylene, after it was cooled, to produce the curing catalystcontaining the active component at 50% (Curing Catalyst 1).

Production Example E4

[Production of Copolymer Containing Acidic Phosphate Ester]

Isopropanol, 170 g and butyl acetate, 170 g were charged in a reactor,equipped with an agitator, a thermometer, a nitrogen-supplying nozzle, adrip-feed funnel and a condenser, and heated at 110° C.

Then, the reactor was continuously charged for 3 hours with a solutionof 200 g of styrene, 300 g of butyl acrylate, 380 g of methylmethacrylate, 110 g of α-acid phosphooxyethyl methacrylate (DaihachiKagaku, MR-200), 20 g of acrylic acid and 30 g ofazobisisobutylonitrile.

On completion of the addition of the monomer, a separately preparedsolution of 3 g of azobisisobutylonitrile dissolved in 200 g of butylacetate was added to the above mixture in 1 hour for the polymerizationfor another 1 hour. It was further incorporated with 350 g ofisopropanol, to produce the copolymer containing acidic phosphate ester,containing resin solid at 50% (Curing Catalyst 2).

Production Example E5

1,9-Decadiene, 138 g was charged in a pressure-resistant reactor, towhich 256 g of trimethoxysilane and 1.04 g of 10% isopropanol solutionof chloroplatinic acid were added in a nitrogen atmosphere, to allowthem to react with each other at 90° C. for 4 hours. On completion ofthe reactions, the product was analyzed by infrared absorptionspectroscopy. Infrared absorption of the allyl group at 1640cm⁻¹ wasfound to disappear. The unreacted trimethoxysilane was distilled off at100° C. under a vacuum (5 Torr), to obtain the silane compound (B-1)having a structure of (CH₃O)₃Si(CH₂)₁₀Si(OCH₃)₃.

Production Example E6

1-Octadecene, 252 g was charged in a pressure-resistant reactor, towhich 142 g of trichlorosilane and 0.5 g of 10% isopropanol solution ofchloroplatinic acid were added in a nitrogen atmosphere, to allow themto react with each other at 90° C. for 4 hours. On completion of thereactions, the product was analyzed by infrared absorption spectroscopy.Infrared absorption of the allyl group at 1640 cm⁻¹ was found todisappear. The unreacted trichlorosilane was distilled off at 100° C.under a vacuum (5 Torr). The effluent was incorporated with 192 g ofmethanol, treated under a vacuum to remove hydrogen chloride gas formed,further subjected to ester exchanging at 60° C. for 2 hours with theaddition of 100 g of methyl orthoformate, and treated under a vacuum (5Torr) to distill of the volatiles, to obtain the silane compound (B-2)having a structure of (CH₃O)₃Si(CH₂)₁₇CH₃.

Production Example E7

1-Octadecanol, 270 g was charged in a pressure-resistant reactor, towhich 14 g of hexane was added, and the mixture was treated fordeaeration under a vacuum (5 Torr) at 90° C. for 1 hour to removemoisture.

It was incorporated with 257 g of γ-isocyanate propyltriethoxysilane ina nitrogen atmosphere, and they were allowed to react with each other at90° C. for 2 hours and then at 110° C. for 1 hour. The product wasanalyzed by infrared absorption spectroscopy. Infrared absorption ofisocyanate at 2270 cm⁻¹ disappeared, and that relevant to the urethanebond was observed at 1530 cm⁻¹. Thus, it is judged that the silanecompound (B-6) having the following structure was formed.

Production Example E8

Hydrogenated polybutadiene glycol, 500 g (Nippon Soda Co., Ltd.,NISSO-PB GI-1000) having a hydroxyl value of 63.6 was charged in apressure-resistant reactor, to which 25 g of hexane was added, and themixture was treated for deaeration under a vacuum (5 Torr) at 90° C. for1 hour to remove moisture.

Next, the above composition was incorporated with 126 g of 28% methanolsolution of sodium methoxide, and the reactants were allowed to reactwith each other for 4 hours, while methanol was distilled off at 140° C.under a vacuum. Then, 52.5 g of allyl chloride was added to the abovesystem dropwise for the reactions at 110° C. for 2 hours. The effluentwas distilled at 110° C. under a vacuum to remove the volatiles. Theeffluent was incorporated with 1.5 L of hexane and 50 g of aluminumsilicate after it was cooled, and the resultant mixture was stirred for1 hour, allowed to stand, filtered by celite to remove the salt, anddistilled under a vacuum to remove hexane, to obtain the hydrogenatedpolybutadiene with allyl groups at both terminals.

Then, 300 g of the above product was charged in a pressure-resistantreactor, to which 15 g of hexane was added, and the mixture was treatedfor deaeration under a vacuum at 90° C. to remove moisture. Next, theabove composition was incorporated with 49.9 g of trimethoxysilane and0.21 g of 10% isopropanol solution of chloroplatinic acid, to allow themto react with each other at 90° C. for 4 hours.

On completion of the reactions, the effluent was distilled at 100° C.under a vacuum to remove the volatiles. This produced the hydrogenatedpolybutadiene with trimethoxysilyl groups at both terminals (SilaneCompound B-3).

Examples E1 to E7

The composition containing the dimethoxymethylsilyl-containingethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1),prepared in PRODUCTION EXAMPLE E1, was prepared for each of EXAMPLES E1to E7. The other components were the silane compound (B) having a longpolyolefin chain prepared in one of PRODUCTION EXAMPLES E5 to E8, andthe curing catalyst (C) prepared in PRODUCTION EXAMPLE E3 or E4, or of acommercial tin compound (dioctyl tin maleate, Sakai Kagaku, TN801™). Thecomposition for each EXAMPLE is given in Table E1. It was diluted withxylene to have an adequate viscosity for a paint.

The coating film of the thermosetting resin was prepared by thefollowing procedure. A soft steel plate was ground by a #240, abrasivepaper, coated with a 2-liquid type urethane surfacer (Isamu Toryo,Hiprisurf 2C™), ground again by a #400 abrasive paper after it wasdried, and coated with a clear paint of melamine acrylic resin (KansaiPaint Co., Ltd., Magiclon M-77™). The coating film was baked at 150° C.for 30 minutes, and treated with a medium rubbing compound, to form thebase.

The coating film of the thermosetting resin was spray-coated with thecomposition prepared in each of EXAMPLES E1 to E7, after it was madeinto the paint, by the common method, forcedly dried at 60° C. for 30minutes, and allowed to stand at room temperature for 7 days, to producethe cured coating film.

Its adhesion was evaluated by a 2 mm square checker pattern cut by aknife, wherein a cellophane tape was put on the pattern and then takenoff, for visual observation of the surface exfoliation conditions.

Then, the test piece was placed in a blister box kept at 50° C. and RH98% for 3 days, and evaluated again for adhesion, based on the standardsprovided by Nippon Paint, Inspection and Testing Association (Point 10:No exfoliation of the coating film, and Point 0: Coating film is totallyexfoliated).

The results are given in Table E1.

TABLE E1 EXAMPLES E1 E2 E3 E4 E5 E6 E7 Dimethoxysilyl-containing EPDM(1) 100 100 100 100 100 100 100 Silane compound (B) having a longpolyolefin chain B-1 (PRODUCTION EXAMPLE E5) 6.5 — — — — — — B-2(PRODUCTION EXAMPLE E6) — 6.5 — — 6.5 6.5 6.5 B-3 (PRODUCTION EXAMPLEE7) — — 6.5 — — — — B-4 (PRODUCTION EXAMPLE E8) — — — 6.5 — — — Curingcatalyst (C) AP-8 * — — — — 1 — — Curing catalyst 1 2 2 2 2 — — —(PRODUCTION EXAMPLE E3) Curing catalyst 2 — — — — — 10 — (PRODUCTIONEXAMPLE E4) TN801 ** — — — — — — 2 Adhesion Primary 10 10 10 10 10 10 10Secondary 10 10 10 10 10 10 10 Curing speed (1A) [Hr] 6 7 8 9 7 8 10(1B) ◯ ◯ ◯ ◯ ◯ ◯ ◯ Resistance to weather *** A A A A A A A * AP-8 (Trademark), Daihachi Kagaku, A mixture of dioctyl phosphate and monooctylphosphate ** TN801 (Trade mark), Sakai Kagaku, Dioctyl tin maleate ***Evaluation of resistance to weather: A: No cracks or molten portionobserved, B: Small cracks or molten portion observed, although slightly,C: Cracks or molten portion observed.

Comparative Examples E1 to E11

The composition containing the silyl-containing vinyl resin, prepared inPRODUCTION EXAMPLE E2, was prepared for each of COMPARATIVE EXAMPLES E1to E11. The other components were the silane compound (B) having a longpolyolefin chain prepared in one of PRODUCTION EXAMPLES E5 to E8, andthe curing catalyst (C) prepared in PRODUCTION EXAMPLE E3 or E4, or of acommercial tin compound (dioctyl tin maleate, Sakai Kagaku, TN801™). Thecomposition for each COMPARATIVE EXAMPLE is given in Table E1 . It wasdiluted with xylene to have an adequate viscosity for a paint.

Each composition was evaluated its adhesion in the same manner as inEXAMPLE E1.

The results are given in Table E2.

The composition prepared in each of EXAMPLES E1 to E7 and COMPARATIVEEXAMPLES E1 to E11 was tested for curing speed and resistance toweather, in accordance with the methods described earlier.

The results are given in Tables E1 and E2.

TABLE E2 COMPARATIVE EXAMPLES E1 E2 E3 E4 E5 E6 E7 E8 E9 E10 E11Silyl-containing vinyl-based resin 100 100 100 100 100 100 100 100 100100 100 (PRODUCTION EXAMPLE E2) Silane compound (B) having a longpolyolefin chain B-1 (PRODUCTION EXAMPLE E5) 6.5 — — — — — — — — — — B-2(PRODUCTION EXAMPLE E6) — 6.5 — — 6.5 6.5 6.5 — — — — B-3 (PRODUCTIONEXAMPLE E7) — — 6.5 — — — — — — — — B-4 (PRODUCTION EXAMPLE E8) — — —6.5 — — — — — — — Curing catalyst (C) AP-8 * — — — — 1 — — 1 — — —Curing catalyst 1 2 2 2 2 — — — — 2 — — (PRODUCTION EXAMPLE E3) Curingcatalyst 2 — — — — — 10 — — — 10 — (PRODUCTION EXAMPLE E4) TN801 ** — —— — — — 2 — — — 2 Adhesion Primary 10 10 10 10 9 8 8 1 2 0 0 Secondary 99 9 9 8 7 7 0 0 0 0 Curing speed (Hr) (1A) 18 20 24 22 14 16 18 24 36 2048 (1B) X X X X X X X X X X X Resistance to weather *** B B B B C C C CC C C * AP-8 (Trade mark), Daihachi Kagaku, A mixture of dioctylphosphate and monooctyl phosphate ** TN801 (Trade mark), Sakai Kagaku,Dioctyl tin maleate *** Evaluation of resistance to weather: A: Nocracks or molten portion observed, B: Small cracks or molten portionobserved, although slightly, C: Cracks or molten portion observed.

Examples F Series

The composition, iodine value, intrinsic viscosity [η] and molecularweight distribution (Mw/Mn) of the copolymer rubber used in each ofEXAMPLES and COMPARATIVE EXAMPLES were determined by the methodsdescribed earlier.

The curing speed tests and the weather resistance tests were conductedby the following methods for EXAMPLES and COMPARATIVE EXAMPLES.

(1) Curing Speed Test

The curable composition (stock material) was cured under the conditionsof 23° C. and 50% RH for 24 hours in a mold, 20 by 80 by 5 mm in size.

Next, the cured product was released from the mold, and thickness of thecured portion was measured by a dial gauge of weak spring force to 0.1mm, to evaluate its curing speed. It was marked with ⊚ when itsthickness was 2 mm or more, Δ when it was 1 to 1.9 mm, and x when it wasless than 0.9 mm.

(2) Weather Resistance Test

The weather resistance test was conducted in accordance with JIS B-7753using a Sunshine Carbon Arc weatherometer.

<Testing Conditions>

-   Light irradiation/rainfall cycles: Irradiation for 120    minutes/rainfall for 18 minutes-   Black panel temperature: 63±2° C.-   Tank inside temperature: 40±2° C.-   Total light irradiation time: 500 hours

Production Example F1

[Production of silyl-containing ethylene/propylene/5-vinyl-2-norborneneRandom Copolymer Rubber (A-1)]

The three-component copolymerization was effected continuously in astainless steel polymerization reactor having an essential capacity of100 L, equipped with agitator blades (agitating rotation speed: 250rpm), wherein hexane, ethylene, propylene and 5-vinyl-2-norbornene werecontinuously supplied at 60 L, 2.5 kg, 4.0 kg and 380 g per hour,respectively, from the reactor side into the liquid phase, and hydrogen,VO(OEt)₂Cl and Al(Et)_(1.5)Cl_(1.5) as the catalysts at 700 L, 45 mmolsand 315 mmols per hour, respectively, also continuously.

The copolymerization effected under the above conditions produced theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A₀-1)in a form of uniform solution.

A small quantity of methanol was added to the polymer solution,continuously withdrawn from the reactor bottom, to terminate thepolymerization. The polymer was separated from the solvent bysteam-stripping the solution, and dried at 55° C. for 48 hours under avacuum.

The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber(A₀-1) thus produced contained ethylene at 68% by mol, and had anintrinsic viscosity [η] of 0.2 dl/g measured in decalin kept at 135° C.,iodine value (IV) of 10(g/100 g) and Mw/Mn of 15.

Two % toluene solution (0.3 g) of chloroplatinic acid and 1.5 g ofmethyldimethoxysilane were added to 100 g of the

-   -   ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber        (A₀-1), and they were allowed to react with each other at        120° C. for 2 hours. The excess methyldimethoxysilane and the        solvent (toluene) were distilled off from the effluent. This        produced 101.5 g of the ethylene/propylene/5-vinyl-2-norbornene        random copolymer rubber (A-1) containing dimethoxymethylsilyl        group (—SiCH₃(OCH₃)₂).

Production Example F2

In a 1 L metallic autoclave, 148 g of phthalic anhydride, 46.4 g ofpropylene oxide, 22.8 g of acrylglycidyl ether, 11.6 g of allyl alcoholand 0.5 g of dimethylbenzylamine were charged and reacted with eachother at 100° C. for 3 hours, to which 46 g of propylene oxide was addedfor further reactions for another 1 hour. Then, the excess propyleneoxide was removed, to obtain the polyester having a molecular weight of1,200.

Next, 100 g of the polyester thus produced was reacted with 9.5 g ofacetic anhydride at 120° C. for 2 hours, and the hydroxyl group in thepolyester was treated, after the excess acetic anhydride was removed.Then 22.2 g of the polyester with the treated hydroxyl group was reactedwith 0.0035 g of chloroplatinic acid and 8.65 g of methyl dichlorosilaneat 80° C. for 3 hours. The excess methyl dichlorosilane was removedunder a vacuum. Then, the above effluent was incorporated with 20 mL ofmethanol and 20 mL of methyl orthoformate, and the mixture was stirredat room temperature for 1 hour to remove the low-boiling materials undera vacuum. This produced the silyl-containing polyester.

Production Example F3

A solution of 2 g of azobisisobutylonitrile dissolved in 30 g ofstyrene, 16 g of allyl methacrylate, 20 g of methyl methacrylate, 19 gof n-butyl methacrylate, 14 g of n-butyl acrylate, 1 g of acrylic acidand 2 g of n-dodecylmercaptan was added dropwise to 100 g of toluene asthe solvent heated at 90° C., and they were allowed to react with eachother for 10 hours, to obtain the vinyl-based polymer having a molecularweight of 8,000 and containing an allyl type unsaturated group.

The vinyl-based polymer had the infrared absorption relevant to thecarbon-carbon double bond at 1648 cm⁻¹.

A solution of 1.5 g of methyldimethoxysilane and 0.0005 g ofchloroplatinic acid dissolved in isopropanol was added to 20 g of thevinyl-based polymer having an allyl type unsaturated group thusproduced, and they were allowed to react with each other at 90° C. for 6hours under sealed conditions. The product had no infrared absorption at1648 cm⁻¹ in the infrared absorption spectral pattern. Therefore, it wasjudged that the silyl-containing vinyl-based polymer was produced.

Production Example F4

The silyl-containing diallyl phthalate-based copolymer was produced inthe same manner as in PRODUCTION EXAMPLE F3, except that 16 g of allylmethacrylate was replaced by 31 g of diallyl phthalate.

Production Example F5

A solution of 2 g of azobisisobutylonitrile dissolved in 30 g ofstyrene, 27 g of γ-methacryloxypropyltrimethoxysilane, 20 g of methylmethacrylate, 19 g of n-butyl methacrylate, 14 g of n-butyl acrylate, 1g of acrylic acid and 2 g of n-dodecylmercaptan was added dropwise to100 g of toluene as the solvent heated at 100° C., and they were allowedto react with each other for 10 hours, to obtain the silyl-containingvinyl-based polymer having a molecular weight of 9,000.

Production Example F6

One hundred grams of diallyl phthalate prepolymer (DAISO Co. Ltd., DAISODAP L™) having an iodine value of around 80, 0.00001 g of chloroplatinicacid and 1 g of hydroquinone were dissolved in 100 mL of toluene, towhich 35mL of methyl diethoxysilane was added, and they were allowed toreact with each other at 90° C. for 3 hours, to obtain thesilyl-containing diallyl phthalate prepolymer.

Production Example F7

[Production of silyl-containing Polymer]

Xylene, 45.9parts by weight was charged in a reactor, equipped with anagitator, a thermometer, a reflux condenser, an N₂ gas-supplying nozzleand a drip-feed funnel, and heated to 110° C. in a flow of N₂ gas, towhich the mixture (a) described below was added dropwise through thedrip-feed funnel at a constant rate for 5 hours:

Mixture (a);

Styrene 12.8 parts by weight Methyl methacrylate 50.1 parts by weightStearyl methacrylate  6.9 parts by weightγ-Methacryloxypropyltrimethoxysilane 30.2 parts by weight Xylene 13.5parts by weight 2,2′-Azobisisobutylonitrile  4.5 parts by weight

On completion of addition of the above mixture (a), 0.5 part by weightof 2,2′-azobisisobutylonitrile and 5 parts by weight of toluene werefurther added at a constant rate for 1 hour. The resultant resinsolution was cured at 110° C. for 2 hours and cooled, to which xylenewas added to adjust the solid content at 60%.

The characteristics of the Resin Solution A thus obtained are given inTable F1.

Production Example F8

[Production of Acrylic-based Resin for Paints]

Resin Solution B was produced in the same manner as in PRODUCTIONEXAMPLE F7, except that 31.8 parts by weight of butyl acetate and 9.5parts by weight of xylene were charged, to which the mixture (b)described below was added in place of the mixture (a):

Mixture (b)

Xylene 18.0 parts by weight Styrene 28.3 parts by weight Methylmethacrylate  6.9 parts by weight n-Butyl acrylate 47.6 parts by weightMethacrylic acid  0.3 part by weight  2-Hydroxyethyl methacrylate 16.9parts by weight 2,2′-Azobisisobutylonitrile  1.8 parts by weight

On completion of addition of the above mixture (b), 0.2 part by weightof 2,2′-azobisisobutylonitrile and 3.8 parts by weight of toluene werefurther added at a constant rate for 1 hour. The resultant resinsolution was cured at 110° C. for 2 hours and cooled, to which xylenewas added to adjust the solid content at 60%.

The characteristics of the Resin Solution B thus obtained are given inTable F1.

TABLE F1 Characteristics Resin Solution A Resin Solution B Non-volatile60 60 matters [%] Viscosity (23° C.) 900 4400 [cPs] Acid value 0 2.0(KOH/g solid) Hydroxyl value 0 73 (KOH/g solid) Color Number <1 <1(Gardner)

Examples F1 to F8, and Comparative Examples F1 to F14

A soft steel plate as the base for the test piece was degreased, groundby a#240 abrasive paper, coated with a urethane surfacer, and baked at80° C. for 30 minutes. Then, the coated surface was further ground by a#600 abrasive paper, coated with a clear paint, described in Table F2for each of EXAMPLES F1 to F8 and COMPARATIVE EXAMPLES F1 to F14, andbaked at 140° C. for30 minutes, to prepare the test piece.

Each test piece was left at room temperature for 30 minutes, after itwas baked under the above conditions. Their characteristics are given inTable F2.

The notes *1 to *4 in Table F2 are described below:

-   *1: Q-631 is a modified cycloaliphatic polyamine, produced by Mitsui    Chemicals, Inc.-   *2: Hardness was determined in accordance with JIS K-5400.-   *3: For the toluene spot test, several drops of toluene were dropped    onto the coating film, left at room temperature and dried, to    observe the coating film conditions.

Resistance of the film to the solvent was evaluated according to thefollowing four-grade system.

<Four-grade System for Evaluation of the Resistance to the Solvent>

⊚: No change is observed at all on the coating film surface

◯: No change is observed on the coating film surface

Δ: Traces are left on the coating film surface

x: The coating film is dissolved

-   *4: Evaluation of resistance to weather-   A: No cracks or molten portion observed.-   B: Small cracks or molten portion observed, although slightly.-   C: Cracks or molten portion observed.

TABLE F2 EXAMPLES F1 F2 F3 F4 F5 F6 F7 F8 Composition [parts by weight]Silyl-Containing Copolymer 100 100 100 100 100 100 100 100 PRODUCTIONEXAMPLE F1 Acrylic Resin 80 — — — — — — — PRODUCTION EXAMPLE F8Thermosetting Acrylic Paint — 80 — — — 80 — 80 (Belcoat No. 5200) Alkydpaint — — 40 — — — — — (Hariphthal SFC42-60X) Epoxy-based paint — — — 40— — — — (Epikote 1001) Organopolysiloxane — — — — 40 — 40 — (Z6018)Amines(B) Q-631 *1 — — — — — 2 2 — Piperidine — — — — — — — 3Monoethanol amine 2 2 2 2 2 — — — Silane-coupling agent (C)N-β-(aminoethyl)-γ-aminopropyl — — — — — 1 1 — trimethoxysilaneγ-aminopropyltriethoxysilane — — — — — — — 1.5γ-mercaptopropyltriethoxysilane 1 1 1 1 1 — — — Tests Hardness *2 3H 3H3H 3H 3H 3H 3H 3H Toluene spot test *3 ◯ to ◯ to ◯ to ◯ to ◯ to ◯ to ◯to ◯ to ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ Curing speed (Film tension) ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚Resistance to weather *4 A A A A A A A A COMPARATIVE EXAMPLES F1 F2 F3F4 F5 F6 F7 Composition [parts by weight] Silyl-Containing CopolymerPRODUCTION EXAMPLE F3 — — — — — 100 100 PRODUCTION EXAMPLE F4 — — — — —— — PRODUCTION EXAMPLE F5 100 100 100 100 100 — — Acrylic Resin 80 — — —— — — PRODUCTION EXAMPLE F8 Thermosetting acrylic paint — 80 — — — 80 —(Belcoat No. 5200) Alkyd paint — — 40 — — — — (Hariphthal SFC42-60X)Epoxy-based paint — — — 40 — — 40 (Epikote 1001) Organopolysiloxane — —— — 40 — — (Z6018) Amines (B) Q-631 *1 — — — — — 2 2 Piperidine — — — —— — — Monoethanolamine 2 2 2 2 2 — — Silane-coupling agent (C)N-β-(aminoethyl)-γ- — — — — — 1 1 aminopropyl-Trimethoxysilaneγ-Aminopropyltriethoxysilane — — — — — — —γ-Mercaptopropyltriethoxysilane 1 1 1 1 1 — — Tests Hardness *2 2H 2H 2H2H 2H 2H 2H Toluene spot test *3 ◯ ◯ ◯ ◯ ◯ ◯ ◯ Curing speed (Filmtension) X X Δ Δ Δ X X Resistance to weather *4 B B B B B B BCOMPARATIVE EXAMPLES F8 F9 F10 F11 F12 F13 F14 Composition [parts byweight] Silyl-Containing Copolymer PRODUCTION EXAMPLE F2 — — — — — — 100PRODUCTION EXAMPLE F3 — — — — — — — PRODUCTION EXAMPLE F4 100 — — — — —— PRODUCTION EXAMPLE F5 — 100 100 — — — — Acrylic Resin PRODUCTIONEXAMPLE F8 — — — — — — 80 Thermosetting acrylic paint (Belcoat No. 5200)80 — 80 180 — — — Alkyd paint (Hariphthal SFC42-60X) — — — — — — —Epoxy-based paint (Epikote 1001) — — — — 140 — — Organopolysiloxane(Z6018) — — — — — 140 — Amines (B) Q-631 *1 — — — — — — — Piperidine 3 —— — — — — Monoethanolamine — 2 — 2 2 2 2 Silane-coupling agent (C)N-β-(aminoethyl)-γ-aminopropyl — — — — — — — trimethoxysilaneγ-aminopropyltriethoxysilane 1.5 — — — — — —γ-mercaptopropyltriethoxysilane — 1 — 1 1 1 1 Tests Hardness *2 2H HB 6B2H 2H 2H 3H Toluene spot test *3 ◯ Δ X ◯ ◯ ◯ ◯ to ⊚ Curing speed (Filmtension) X X X X X X ⊚ Resistance to weather *4 B C C B to C B to C B toC C

Reference Examples F1 to F5, and Reference Comparative Examples F1 to F5

A soft steel plate as the base for the test piece was degreased, groundby a #240 abrasive paper, coated with a urethane surfacer, and baked at80° C. for 30 minutes. Then, the coated surface was further ground by a#600 abrasive paper, coated with a clear paint, described in Table F3for each of REFERENCE EXAMPLES F1 to F5 and REFERENCE COMPARATIVEEXAMPLES F1 to F5, and baked at 140° C. for 30 minutes, to prepare thetest piece.

Each test piece was left at room temperature for 30 minutes, after itwas baked under the above conditions. Their characteristics are given inTable F3.

The notes *1 to *11 in Table F3 are described below:

-   *1 : Thermosetting acrylic paint, produced by NOF Corp.-   *2 : Soybean fatty acid short-oil type alkyd resin, produced by    Harima Chemicals.-   *3 : Epoxy resin, produced by Shell-   *4 : Organopolysiloxane, produced by Dow Corning-   *5 : Dioctyl tin maleate, Sakai Kagaku Kogyo-   *6 : Amino-containing silane coupling agent, produced by UCC-   *7 : Epoxy-containing silane coupling agent, produced by UCC-   *8 : Dioctyl acid phosphate, produced by Daihachi Kagaku-   *9 : Hardness was determined in accordance with JIS K-5400-   *10 : For the toluene spot test, several drops of toluene was    dropped onto the coating film, left at room temperature and dried,    to observe the coating film conditions. Resistance of the film to    the solvent was evaluated according to the following four-grade    system.

<Four-grade System for Evaluation of the Resistance to the Solvent>

-   -   ⊚: No change is observed at all on the coating film surface    -   ◯: No change is observed on the coating film surface    -   Δ: Traces are left on the coating film surface    -   x: The coating film is dissolved

-   *11 : Evaluation of resistance to weather    -   A: No cracks or molten portion observed    -   B: Small cracks or molten portion observed, although slightly    -   C: Cracks or molten portion observed

TABLE F3 REFERENCE EXAMPLE F1 F2 F3 F4 F5 Composition [parts by weight]Silyl-Containing Copolymer 100 100 100 100 100 PRODUCTION EXAMPLE F7Acrylic Resin 80 — — — — PRODUCTION EXAMPLE F8 Thermosetting acrylicpaint — 80 — — — (Belcoat No. 5200, Clear S) *1 Alkyd paint — — 40 — —(Hariphthal SFC42-60X) *2 Epoxy-based paint — — — 40 — (Epikote 1001) *3Organopolysiloxane — — — — 40 (Z6018) *4 Curing catalysts TN801 *5 4 4 —— — A-1120 *6 1 1 — — — A-187 *7 1 1 — — — DP-8 *8 — — 1 1 1N,N-dimethyl-n-dodecylamine — — 1 1 1 Tests Hardness *9 2H 2H 2H 2H 2HToluene spot test *10 ◯ ◯ ◯ ◯ ◯ Curing speed (Film tension) X X X X XResistance to weather *11 B B B B B REFERENCE COMPARATIVE EXAMPLE F1 F2F3 F4 F5 Composition [parts by weight] Silyl-Containing Copolymer 100100 — — — PRODUCTION EXAMPLE F7 Acrylic Resin — 80 — — — PRODUCTIONEXAMPLE F8 Thermosetting acrylic paint — — 180 — — (Belcoat No. 5200,Clear S) *1 Alkyd paint — — — — — Hariphthal SFC42-60X) *2 Epoxy-basedpaint — — — 140 — (Epikote 1001) *3 Organopolysiloxane — — — — 140(Z6018) *4 Curing catalysts TN801 *5 4 — 4 — — A-1120 *6 1 — 1 — — A-187*7 1 — 1 — — DP-8 *8 — — — 1 1 N,N-dimethyl-n-dodecylamine — — — 1 1Tests Hardness *9 HB 6B 2H 2H 2H Toluene spot test *10 Δ X ◯ ◯ ◯ Curingspeed (Film tension) X X X X X Resistance to weather *11 C C C C C

Examples G Series

The composition, iodine value, intrinsic viscosity [η] and molecularweight distribution (Mw/Mn) of the copolymer rubber used in each ofEXAMPLES and COMPARATIVE EXAMPLES were determined by the methodsdescribed earlier.

Production Example

[Production of silyl-containing ethylene/propylene/5-vinyl-2-norborneneRandom Copolymer Rubber (A-1)]

The three-component copolymerization was effected continuously in astainless steel polymerization reactor having an essential capacity of100 L, equipped with agitator blades (agitating rotation speed: 250rpm), wherein hexane, ethylene, propylene and 5-vinyl-2-norbornene werecontinuously supplied at 60 L, 2.5 kg, 4.0 kg and 380 g per hour,respectively, from the reactor side into the liquid phase, and hydrogen,VO(OEt)₂Cl and Al(Et)_(1.5)Cl_(1.5) as the catalysts at 700 L, 45 mmolsand 315 mmols per hour, respectively, also continuously.

The copolymerization effected under the above conditions produced theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A₀-1)in a form of uniform solution.

A small quantity of methanol was added to the polymer solution,continuously withdrawn from the reactor bottom, to terminate thepolymerization. The polymer was separated from the solvent bysteam-stripping the solution, and dried at 55° C. for 48 hours under avacuum.

The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber(A₀-1) thus produced contained ethylene at 68% by mol, and had anintrinsic viscosity [η] of 0.2 dl/g measured in decalin kept at 135° C.,iodine value (IV) of 10 (g/100 g) and Mw/Mn of 15.

Two % toluene solution (0.3 part by weight) of chloroplatinic acid and1.5 parts by weight of methyldimethoxysilane were added to 100 parts byweight of the ethylene/propylene/5-vinyl-2-norbornene random copolymerrubber (A₀-1), and they were allowed to react with each other at 120° C.for 2 hours. The excess methyldimethoxysilane and the solvent (toluene)were distilled off from the effluent. This produced 101.5 parts byweight of the ethylene/propylene/5-vinyl-2-norbornene random copolymerrubber (A-1) containing dimethoxymethylsilyl group (—Si (CH₃) (OCH₃)₂).

Examples G1to G8, and Reference Example G1

A mixture containing the silyl-containingethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1),prepared in PRODUCTION EXAMPLE, was prepared for each of the aboveexamples. It was composed of 100 g of the copolymer rubber (A-1), 120 gof calcium carbonate as the filler (Shiraishi K. K., CCR™), 20 g oftitanium dioxide (Ishihara Sangyo Kaisha, Ltd., R820™), 2 g of dibutyltin diacetylacetonate (NITTO KASEI, U-220™) as the curing promoter, 50 gof a paraffin-based process oil as the plasticizer (Idemitsu Kosan,Diana Process Oil PW-380™) for EXAMPLES G1 to G8 and REFERENCE, EXAMPLEG1, 2 g of a monovalent silanol compound shown in Table G1, andN-(β-aminoethyl)-γ-aminopropyltrimethoxy silane (H₂NCH₂CH₂NHCH₂CH₂CH₂Si(OCH₃)₃) and N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane(NH₂CH₂CH₂NHCH₂CH₂CH₂Si (CH₃) (OCH₃)₂) as the trifunctional andbifunctional aminosilane compound, respectively, in a quantity shown inTable G1. It was sufficiently kneaded to mix the components by a 3-paintroll unit, and put in the H-shape test piece prepared in accordance withJIS A-5758, to determine its tensile characteristics, adhesion strengthand resistance of the adhesion strength to weather while the test piecewas irradiated with light (weather-resistant adhesion). It was alsoanalyzed for its curing speed and resistance to weather (ozone-causedaging test). The results are given in Table G1. The following testingmethods were used.

(Tensile Characteristics)

The composition thus prepared was put in the H-shape test piece preparedin accordance with JIS A-5758 (base: anodized aluminum oxide), which wascured at 23° C. and RH60% for 14 days, and further cured at 30° C. for14 days, to be tensile-tested at a speed of 30 mm/minute.

(Adhesion Strength)

The test piece, when fractured in the tensile test, was observed for thefractured conditions.

It is judged to have a high adhesion strength to the base, when thecured product itself was fractured (cohesion fracture, CF), and a lowadhesion strength when the cured product and base were separated fromeach other at the adhesion interface (adhesion fracture, AF)(Weather-resistant Adhesion)

The H-shape test piece (base: glass) was prepared in accordance with JISA-5758, irradiated with light for 480 hours for accelerated exposuretest by a Sunshine weatherometer (Suga Shikenki, WEL-3-HC), andtensile-tested by an Autograph (Shimadzu, IS-5000).

(Curing Speed Test)

The curable composition was cured under the conditions of 23° C. and 50%RH for 24 hours in a mold, 20 by 80 by 5 mm in size.

Next, the cured product was released from the mold, and thickness of thecured portion was measured by a dial gauge of weak spring force to 0.1mm, to evaluate its curing speed. It was marked with ◯ when itsthickness was more than 1 mm, Δ when it was 0.5 to 1 mm, and x when itwas less than 0.5 mm.

(Weather Resistance Test)

The accelerated weather resistance test was conducted in accordance withJIS B-7753 under the following conditions.

-   Analyzer: Sunshine Carbon Arc weatherometer-   Light irradiation/rainfall cycles: Irradiation for 120    minutes/rainfall for 18 minutes-   Black panel temperature: 63±2° C.-   Tank inside temperature: 40±2° C.-   Total light irradiation time: 500 hours

The tested test piece was visually observed, to evaluate its resistanceto weather according to the following four grades:

-   ⊚: No cracks or molten portion observed-   ◯: Cracks or molten portion observed, although slightly-   Δ: Cracks or molten portion observed to some extent-   x: Cracks or molten portion observed significantly

TABLE G1 Trifunctional H type tensile Monovalent Aminosilane (g)characteristics silanol-based Bifunctional M₁₅₀ T_(B) E_(B) compoundAminosilane (g) (kg/cm²) (kg/cm²) (%) EXAMPLEG1

0.53.0 2.0 8.9 550 EXAMPLE (CH₃)₃Si—NH—Si(CH₃)₃ 1.0 2.4 8.5 530 G2 3.0EXAMPLE (CH₃)₃Si—O—C₆H₅ 0.5 2.6 8.4 560 G3 3.0 EXAMPLE — 0.5 3.9 8.6 520G4 3.0 EXAMPLE (CH₃)₃Si—NH—Si(CH₃)₃ 3.0 5.8 9.4 320 G5 0 EXAMPLE(CH₃)₃Si—NH—Si(CH₃)₃ 0 2.8 8.2 450 G6 3.0 REFERENCE (CH₃)₃SI—NH—Si(CH₃)₃0 4.9 — — EXAMPLE 0 G1 EXAMPLE — 0 5.1 — — G7 3.0 EXAMPLE — 3.0 6.2 — —G8 0 Adhesive Weather-resistant strength adhesion to T_(B) E_(B)Adhesion Curing Resistance to aluminum (kg/cm²) (%) conditions speedweather EXAMPLE CF 8.7 530 CF ◯ ⊚ G1 EXAMPLE CF 8.3 510 CF ◯ ⊚ G2EXAMPLE CF 8.2 530 CF ◯ ⊚ G3 EXAMPLE CF 8.2 500 CF Δ ◯ G4 EXAMPLE CF 8.9290 CF ◯ ◯ G5 EXAMPLE CF 7.9 400 AF ◯ ◯ G6 REFERENCE AF — — AF ◯ ◯EXAMPLE G1 EXAMPLE AF — — AF Δ ◯ G7 EXAMPLE AF — — AF Δ ◯ G8

In the table, the bar “-” was for a test piece with the compositionseparated from the base and the properties of the cured product itselfwere immeasurable.

The comprehensive evaluation results of the compositions prepared inEXAMPLES G1to G8 and REFERENCE EXAMPLE G1 are given in Table G2, whereinthose marked with ◯ have good characteristics, x have not and Δ arein-between.

TABLE G2 Trifunctional Monovalent aminosilane (g) silanol-basedBifunctional Adhesive Weather-resistant Curing Resistance to compoundaminosilane(g) Modulus strength adhesion speed weather EXAMPLE G1 Used0.5/3.0 ◯ ◯ ◯ ◯ ◯ EXAMPLE G2 Used 1.0/3.0 ◯ ◯ ◯ ◯ ◯ EXAMPLE G3 Used0.5/3.0 ◯ ◯ ◯ ◯ ◯ EXAMPLE G4 Not used 0.5/3.0 Δ ◯ ◯ Δ Δ EXAMPLE G5 Used3.0/0   X ◯ ◯ Δ Δ REFERENCE Used   0/3.0 ◯ ◯ X Δ Δ EXAMPLE G1 EXAMPLE G6Used 0/0 X X X Δ Δ EXAMPLE G7 Not used   0/3.0 X X X Δ Δ EXAMPLE G8 Notused 3.0/0   X X X Δ Δ

Comparative Production Example

Eight hundred g of a polyoxypropylene-based polymer, with allyl ethergroup at 97% of the total terminals and having an average molecularweight of around 8,000, was charged in a pressure-resistant reactorequipped with an agitator, to which 19 g of methyldimethoxysilane wasadded. The mixture was then incorporated with 0.34 mL of a solution ofchloroplatinic acid (H₂PtCl₆.6H₂O), 8.9 g dissolved in 18 mL ofisopropyl alcohol and 160 mL of tetrahydrofuran, and they were allowedto react with each other at 80° C. for 6 hours.

The quantitative analysis by IR spectroscopy indicated that thehydrogenated silicon group little remained in the reaction solution. Thequantitative analysis of the reactive silicon group by NMR indicatedthat the polyoxypropylene-based polymer (CA-1) produced hadapproximately 1.7 groups represented by the following formula on theaverage in one molecule at the terminal.

Reference Examples G2 to G10

The curable composition was prepared for each of REFERENCE EXAMPLES G2to G10 in the same manner as in EXAMPLES G1 to G8 and REFERENCE EXAMPLEG1, except that the silyl-containingethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1)was replaced by the polymer (CA-1) prepared in COMPARATIVE PRODUCTIONEXAMPLE, and the paraffin-based process oil as the plasticizer (IdemitsuKosan, Diana Process Oil PW-380™) was replaced by the oxypropylenepolymer of the allyl ether type at the terminal, having an Mn of 5,200and Mw/Mn of 1.6 for REFERENCE EXAMPLES G2 to G3 and G5 to G10), or(2-ethylhexyl) phthalate (Daihachi Kagaku) for REFERENCE EXAMPLE G4. Thecharacteristics of these compositions were evaluated. The results aregiven in Table G3.

TABLE G3 Trifunctional H type tensile Monovalent aminosilane (g)characteristics silanol-based Bifunctional M₁₅₀ T_(B) E_(B) compoundaminosilane (g) (kg/cm²) (kg/cm²) (%) REFERENCEEXAMPLEG2

0.12.0 2.9 8.3 460 REFERENCE (CH₃)₃Si—NH—Si(CH₃)₃ 0.5 2.9 7.9 420EXAMPLE 2.0 G3 REFERENCE (CH₃)₃Si—O—C₆H₅ 0.5 2.8 7.8 440 EXAMPLE 2.0 G4REFERENCE — 0.5 3.9 8.2 460 EXAMPLE 2.0 G5 REFERENCE(CH₃)₃Si—NH—Si(CH₃)₃ 2.0 5.3 9.1 330 EXAMPLE 0 G6 REFERENCE(CH₃)₃Si—NH—Si(CH₃)₃ 0 2.8 8.1 440 EXAMPLE 2.0 G7 REFERENCE(CH₃)₃Si—NH—Si(CH₃)₃ 0 — (2.0)  (90) EXAMPLE 0 G8 REFERENCE — 0 4.7 9.2400 EXAMPLE 2.0 G9 REFERENCE — 2.0 5.8 9.6 320 EXAMPLE 0 G10 AdhesiveWeather-resistant strength adhesion to T_(B) E_(B) Adhesion CuringResistance to aluminum (kg/cm²) (%) conditions speed weather REFERENCECF 8.0 420 CF ◯ Δ or X EXAMPLE G2 REFERENCE CF 7.7 400 CF ◯ Δ or XEXAMPLE G3 REFERENCE CF 7.2 380 CF ◯ Δ or X EXAMPLE G4 REFERENCE CF 8.1440 CF Δ X EXAMPLE G5 REFERENCE CF 8.9 300 CF ◯ X EXAMPLE G6 REFERENCECF (1.9) (120) AF ◯ X EXAMPLE G7 REFERENCE AF (0.9)  (60) AF ◯ X EXAMPLEG8 REFERENCE CF (1.5) (110) AF Δ X EXAMPLE G9 REFERENCE CF 8.1 290 CF ΔX EXAMPLE G10

In the table, the value in the parentheses ( ) was for a test piece withthe composition separated from the base at the adhesion interface, andconsequently the properties are not of the cured product itself.

The comprehensive evaluation results of the compositions prepared inEXAMPLES G2 to G10 are given in Table G4, wherein those marked with ◯have good characteristics, x have not and Δ are in-between.

TABLE G4 Trifunctional Monovalent Aminosilane (g) silanol-basedBifunctional Adhesive Weather-resistant Curing Resistance to compoundAminosilane (g) Modulus strength adhesion speed weather REFERENCE 2 Used0.1/2.0 ◯ ◯ ◯ X X EXAMPLE G 3 Used 0.5/2.0 ◯ ◯ ◯ X X 4 Used 0.5/2.0 ◯ ◯◯ X X 5 Not used 0.5/2.0 X ◯ ◯ X X 6 Used 2.0/0   X ◯ ◯ X X 7 Used  0/2.0 ◯ ◯ X X X 8 Used 0/0 — X X X X 9 Not used   0/2.0 X ◯ X X X 10Not used 2.0/0   X ◯ ◯ X X

Examples H Series

The composition, iodine value, intrinsic viscosity [η] and molecularweight distribution (Mw/Mn) of the copolymer rubber used in each ofEXAMPLE and COMPARATIVE EXAMPLE were determined by the methods describedearlier.

Production Example

[Production of silyl-containing ethylene/propylene/5-vinyl-2-norborneneRandom Copolymer Rubber (A-1)]

The three-component copolymerization was effected continuously in astainless steel polymerization reactor having an essential capacity of100 L, equipped with agitator blades (agitating rotation speed: 250rpm), wherein hexane, ethylene, propylene and 5-vinyl-2-norbornene werecontinuously supplied at 60 L, 2.5 kg, 4.0 kg and 380 g per hour,respectively, from the reactor side into the liquid phase, and hydrogen,VO(OEt)₂Cl and Al(Et)_(1.5)Cl_(1.5) as the catalysts at 700 L, 45 mmolsand 315 mmols per hour, respectively, also continuously.

The copolymerization effected under the above conditions produced theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A₀-1)in a form of uniform solution.

A small quantity of methanol was added to the polymer solution,continuously withdrawn from the reactor bottom, to terminate thepolymerization. The polymer was separated from the solvent bysteam-stripping the solution, and dried at 55° C. for 48 hours under avacuum.

The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber(A₀-1) thus produced contained ethylene at 68% by mol, and had anintrinsic viscosity [η] of 0.2 dl/g measured in decalin kept at 135° C.,iodine value (IV) of 10(g/100 g) and Mw/Mn of 15.

Two % toluene solution (0.3 part by weight) of chloroplatinic acid and1.5 parts by weight of methyldimethoxysilane were added to 100 parts byweight of the ethylene/propylene/5-vinyl-2-norbornene random copolymerrubber (A₀-1), and they were allowed to react with each other at 120° C.for 2 hours. The excess methyldimethoxysilane and the solvent (toluene)were distilled off from the effluent. This produced 101.5 parts byweight of the ethylene/propylene/5-vinyl-2-norbornene random copolymerrubber (A-1) containing dimethoxymethylsilyl group (—Si (CH₃) (OCH₃)₂).

Example H1 and Comparative Example H1

The one-liquid type curable composition was prepared using thesilyl-containing ethylene/propylene/5-vinyl-2-norbornene randomcopolymer rubber (A-1) prepared in PRODUCTION EXAMPLE, to evaluate itsstorage stability and resistance of the cured product to weather. Theircompositions are given in Table H1 (parts by weight), and the evaluationresults in Table H2.

It was evaluated by the following methods.

(Viscosity and Curing Speed (Tack-free Time))

These were determined in accordance with JIS A-5758.

(Curing Speed Test)

The curable composition was cured under the conditions of 23° C. and 50%RH for 24 hours in a mold, 20 by 80 by 5 mm in size.

Next, the cured product was released from the mold, and thickness of thecured portion was measured by a dial gauge of weak spring force to 0.1mm, to evaluate its curing speed. It was marked with ◯ when itsthickness was 1 mm or more and x when it was less than 1.0 mm.

(Weather Resistance Test)

The accelerated weather resistance test was conducted in accordance withJIS B-7753 under the following conditions.

-   Analyzer: Sunshine Carbon Arc weatherometer-   Light irradiation/rainfall cycles: Irradiation for 120    minutes/rainfall for 18 minutes-   Black panel temperature: 63±2° C.-   Tank inside temperature: 40±2° C.-   Total light irradiation time: 500 hours

The tested test piece was visually observed, to evaluate its resistanceto weather according to the following two-grade system: ◯: No cracks ormolten portion observed, and x: Cracks or molten portion observed.

(Storage Stability)

Storage stability of the curable composition was evaluated by viscosity,i.e., ratio of viscosity of the composition stored at 50° C. for 4 weeksin a nitrogen-purged container to that of the one immediately after itswas prepared.

The composition having the ratio closer to unity (1) means it is moreexcellent in storage stability.

Reference Examples H1to H3

The one-liquid type curable composition was prepared for each ofREFERENCE EXAMPLES H1to H3 using the oxypropylene polymer having around2 dimethoxymethylsilyl groups (—Si (CH₃)(OCH₃)₂) in the molecule and anaverage molecular weight of 9,000 (KANEKA CORP., MS Polymer, hereinafterreferred to as CA-1) and oxypropylene polymer having around 1.5dimethoxysilyl groups in the molecule and an average molecular weight of8,000 (KANEKA CORP., MS Polymer, hereinafter referred to as CA-2), andevaluated in the same manner as in EXAMPLE H1. Their compositions aregiven in Table H1 (parts by weight), and the evaluation results in TableH2.

TABLE H1 COMPARATIVE REFERENCE REFERENCE REFERENCE EXAMPLE EXAMPLEEXAMPLE EXAMPLE EXAMPLE Components H1 H1 H1 H2 H3 Polymer rubber A-1 100100 0 0 0 CA-1 0 0 50 50 50 CA-2 0 0 50 50 50 Filler Colloidal calcium120 120 120 120 120 Carbonate*1 Titanium oxide*2 20 20 20 20 20Plasticizer Paraffin-based oil*3 50 50 50 50 50 Dehydrator VTMO*4 3 3 33 3 Tackifier DAMO*5 2 2 2 2 2 Curing catalyst U-220*6 1 1 1 1 1 Organiccarboxylic 2-Ethylhexanoic acid 0.2 0 0.2 0 0 acid Stearic acid 0 0 00.4 0 *1CALFORT-S (STURGE) *2TIOFWE R85 (TDF) *3Paraffin-based oil(Idemitsu Kosan, Diana Process Oil PW-3 ™) *4DYNASYLAN VTMO (Huls)*5DYNASYLAN DAMO (Huls) *6Dibutyl tin diacetylacetate (NITTO KAGAKU)

TABLE H2 EXAMPLE COMPARATIVE REFERENCE REFERENCE REFERENCECharacteristics H1 EXAMPLE H1 EXAMPLE H1 EXAMPLE H2 EXAMPLE H3Immediately after the test Viscosity (Poise) 12000 11000 13000 110009500 piece was prepared Tack-free time (hr) 4 2.5 5.5 4.5 2.5 Curingspeed ◯ ◯ ◯ ◯ ◯ Resistance to weather ◯ ◯ X X X After the test piece wasstored Viscosity (Poise) 14000 15000 13000 13000 13000 at 50° C. forfour weeks Tack-free time (hr) 4 8 5.5 5.0 >10 Curing speed ◯ ◯ ◯ ◯ XResistance to weather ◯ ◯ X X X Storage stability Viscosity ratio 1.171.36 1.18 1.18 1.37

Examples J Series

The composition, iodine value, intrinsic viscosity [η] and molecularweight distribution (Mw/Mn) of the copolymer rubber used in each ofEXAMPLE and EXAMPLE were determined by the methods described earlier.

The curing speed tests and accelerated weather resistance tests wereconducted by the following methods for EXAMPLES and REFERENCE EXAMPLES.

(1) Curing Speed Test

The curable composition (stock material) was cured under the conditionsof 23° C. and 50% RH for 24 hours in a mold, 20 by 80 by 5 mm in size.

Next, the cured product was released from the mold, and thickness of thecured portion was measured by a dial gauge of weak spring force to 0.1mm, to evaluate its curing speed. It was marked with ◯ when itsthickness was 1 mm or more, and x when it was less than 1 mm.

(2) Accelerated Weather Resistance Test

The weather resistance test was conducted in accordance with JIS B-7753using a Sunshine Carbon Arc weatherometer.

<Testing Conditions>

-   Light irradiation/rainfall cycles: Irradiation for 120    minutes/rainfall for 18 minutes-   Black panel temperature: 63±2° C.-   Tank inside temperature: 40±2° C.-   Total light irradiation time: 500 hours-   Property measurements: in accordance with JIS K-6301

Production Example J1

[Production of silyl-containing ethylene/propylene/5-vinyl-2-norborneneRandom Copolymer Rubber (A-1)]

The three-component copolymerization was effected continuously in astainless steel polymerization reactor having an essential capacity of100 L, equipped with agitator blades (agitating rotation speed: 250rpm), wherein hexane, ethylene, propylene and 5-vinyl-2-norbornene werecontinuously supplied at 60 L, 2.5 kg, 4.0 kg and 380 g per hour,respectively, from the reactor side into the liquid phase, and hydrogen,VO(OEt)₂Cl and Al(Et)_(1.5)Cl_(1.5) as the catalysts at 700 L, 45 mmolsand 315 mmols per hour, respectively, also continuously.

The copolymerization effected under the above conditions produced theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A₀-1)in a form of uniform solution.

A small quantity of methanol was added to the polymer solution,continuously withdrawn from the reactor bottom, to terminate thepolymerization. The polymer was separated from the solvent bysteam-stripping the solution, and dried at 55° C. for 48 hours under avacuum.

The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber(A₀-1) thus produced contained ethylene at 68% by mol, and had anintrinsic viscosity [η] of 0.2 dl/g measured in decalin kept at 135° C.,iodine value (IV) of 10(g/100 g) and Mw/Mn of 15.

Two % toluene solution (0.3 g) of chloroplatinic acid and 1.5 g ofmethyldimethoxysilane were added to 100 g of theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A₀-1),and they were allowed to react with each other at 120° C. for 2 hours.The excess methyldimethoxysilane and the solvent (toluene) weredistilled off from the effluent. This produced 101.5 g of theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1)containing dimethoxymethylsilyl group (—SiCH₃(OCH₃)₂)

Production Example J2

Methyl methacrylate, 0.2 mol, allyl methacrylate, 0.086 mol andn-dodecyl mercaptan, 5 g were dissolved in 70 mL of toluene, to which0.5 g of azobisisobutylonitrile was added, and they were allowed toreact with each other at 80° C. for 4 hours (the toluene solution couldbe directly used for the subsequent hydrosilylation). The solvent wasdistilled off under a vacuum, in order to obtain the acrylic-basedpolymer having a molecular weight of around 2,000 and containing anallyl type unsaturated group.

The far-infrared absorption spectroscopic analysis indicated that theacrylic-based polymer thus produced had the absorption relevant to thecarbon-carbon double bond at 1648 cm⁻¹, in addition to the strongabsorption relevant to the ester at 1730 cm⁻¹.

Production Example J3

Methyl methacrylate, 0.2 mol, allyl acrylate, 0.086 mol and n-dodecylmercaptan, 5 g were dissolved in 70 mL of toluene, to which 0.5 g ofazobisisobutylonitrile was added, and they were allowed to react witheach other at 80° C. for 4 hours. This produced the acrylic-basedpolymer having a molecular weight of around 2,000 and containing anallyl type unsaturated group.

The far-infrared absorption spectroscopic analysis indicated that theacrylic-based polymer thus produced had the absorption relevant to thecarbon-carbon double bond at 1648 cm⁻¹.

Production Example J4

Methyl methacrylate, 0.1 mol, styrene, 0.1 mol, allyl methacrylate,0.086 mol and n-dodecyl mercaptan, 5 g were dissolved in 70 mL oftoluene, to which 0.5 g of azobisisobutylonitrile was added, and theywere allowed to react with each other at 80° C. for 4 hours. Thisproduced the vinyl copolymer having a molecular weight of around 2,000.

The far-infrared absorption spectroscopic analysis indicated that thecopolymer thus produced also had the absorption relevant to thecarbon-carbon double bond at 1648 cm⁻¹.

Example J1

A mixture composed of 100 parts by weight of theethylene/propylene/5-vinyl-2-norbornene random copolymer rubbercontaining the hydrolyzable silyl group (A-1), prepared in PRODUCTIONEXAMPLE J1, 10 parts by weight of methanol (B-1) and 4 parts by weightof methyl orthoformate (B-2) was stirred 3 times at 10,000 rpm each for10 minutes by a homogenizer (Nihon Seiki Sesakusho Co., Ltd. Excel AutoHomogenizer), to prepare the composition. It was tested for storagestability at room temperature, after it was diluted to 35% by tolueneand incorporated with 2,000 ppm of moisture. The results are given inTable J2 for the test piece stored for 3 weeks.

Reference Example J1

Methyl dichlorosilane, 1.6 mL and chloroplatinic acid, 0.00001 g wereadded to 20 g of the toluene solution of the acrylic-based polymer,prepared in PRODUCTION EXAMPLE J2, and they were allowed to react witheach other at 90° C. for 3 hours under sealed conditions. The effluentwas incorporated with 5 mL of methanol and 5 mL of methyl orthoformate,and the mixed solution was continuously stirred until the solutionbecame neutral.

The hydrosilylated product had an infrared absorption spectral patternin which the infrared absorption at 1648 cm⁻¹ had completelydisappeared.

The gas chromatography analysis results of the polymer solution aregiven in Table J1.

TABLE J1 1 Gas chromatographic analysis results of the polymer solutionMethyltrimethoxy silane 3.8% Methyl orthoformate 5.0% Methanol 10.5%

The polymer solution thus prepared was tested for storage stability atroom temperature, after it was diluted to 35% by toluene andincorporated with 2,000 ppm of moisture. The results are given in TableJ2 for the test piece stored for 3 weeks.

TABLE J2 Viscosity * (23° C.; cPs) Viscosity changes Initial After 21days (21 days/Initial) EXAMPLE J1 300 520 1.7 REFERENCE 10 21 2.1EXAMPLE J1 * Viscosity was determined by a B type viscometer at 23° C.

As shown in Table J2, the compositions prepared in EXAMPLE J1 andREFERENCE EXAMPLE J1 are excellent in storage stability.

Reference Example J2

The hydrosilylation was effected in the same manner as in REFERENCEEXAMPLE J1, except that 1.6 mL of methyl dichlorosilane was replaced by1.8 mL of methyl diethoxysilane. The hydrosilylated product also had aninfrared absorption spectral pattern in which the infrared absorption at1648 cm⁻¹ had completely disappeared, from which it was judged thatsilyl-containing acrylic-based polymer was produced.

Reference Examples J3 and J4

The hydrosilylation was effected in exactly the same manner as inREFERENCE EXAMPLE J1 for each of the above examples, except that thecopolymer rubber (A-1) was replaced by the polymer prepared inrespective PRODUCTION EXAMPLE J3 and J4, to prepare the resin curable atnormal temperature.

Reference Examples J5 to J8

Two parts by weight of dibutyl tin maleate was added to 100 parts byweight of the resin prepared in each of REFERENCE EXAMPLES J1 to J4, andeach composition was spread over a soft steel plate, to evaluate itscapacity of forming a coating film and other characteristics. Theresults are given in Table J3.

TABLE J3 Time for which the Tack-free test piece was left Resin Time[minutes] * [hrs] Surface gloss * EXAMPLE J1 20 48 Excellent REFERENCE30 48 Excellent EXAMPLE J1 ** 35 48 Excellent REFERENCE 40 48 ExcellentEXAMPLE J2 REFERENCE 30 48 Excellent EXAMPLE J3 REFERENCE 45 72Excellent EXAMPLE J4 * Left at 25° C. and RH 70% ** Resin prepared inREFERENCE EXAMPLE J1 which was further incorporated with 30% by weightof ethyl silicate

Moreover, each composition prepared in EXAMPLE J1 and REFERENCE EXAMPLESJ5 to J8 was tested for curing speed, and the cured product forresistance to weather, in accordance with the methods described earlier.The results are given in Table J4.

TABLE J4 Resistance Curing speed to weather EXAMPLE J1 ◯ No cracksobserved REFERENCE X Cracks observed EXAMPLE J5 slightly REFERENCE XCracks observed EXAMPLE J6 slightly REFERENCE X Cracks observed EXAMPLEJ7 slightly REFERENCE X Cracks observed EXAMPLE J8 slightly

Examples K Series

The composition, iodine value, intrinsic viscosity [η] and molecularweight distribution (Mw/Mn) of the copolymer rubber used in each ofEXAMPLES and REFERENCE EXAMPLES were determined by the methods describedearlier.

The curing speed tests and accelerated weather resistance tests wereconducted by the following methods for EXAMPLES and REFERENCE EXAMPLES.

(1) Curing Speed Test

The curable composition (stock material) was cured under the conditionsof 23° C. and 50% RH for 24 hours in a mold, 20 by 80 by 5 mm in size.

Next, the cured product was released from the mold, and thickness of thecured portion was measured by a dial gauge of weak spring force to 0.1mm, to evaluate its curing speed. It was marked with ◯ when itsthickness was 5 mm or more, and x when it was less than 5 mm.

(2) Accelerated Weather Resistance Test

The weather resistance test was conducted in accordance with JIS B-7753using a Sunshine Carbon Arc weatherometer.

<Testing Conditions>

-   Light irradiation/rainfall cycles: Irradiation for 120    minutes/rainfall for 18 minutes-   Black panel temperature: 63±2° C.-   Tank inside temperature: 40±2° C.-   Total light irradiation time: 500 hours

Production Example K1

[Production of silyl-containing ethylene/propylene/5-vinyl-2-norborneneRandom Copolymer Rubber (A-1)]

The three-component copolymerization was effected continuously in astainless steel polymerization reactor having an essential capacity of100 L, equipped with agitator blades (agitating rotation speed: 250rpm), wherein hexane, ethylene, propylene and 5-vinyl-2-norbornene werecontinuously supplied at 60 L, 2.5 kg, 4.0 kg and 380 g per hour,respectively, from the reactor side into the liquid phase, and hydrogen,VO(OEt)₂Cl and Al(Et)_(1.5)Cl_(1.5) as the catalysts at 700 L, 45 mmolsand 315 mmols per hour, respectively, also continuously.

The copolymerization effected under the above conditions produced theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A₀-1)in a form of uniform solution.

A small quantity of methanol was added to the polymer solution,continuously withdrawn from the reactor bottom, to terminate thepolymerization. The polymer was separated from the solvent bysteam-stripping the solution, and dried at 55° C. for 48 hours under avacuum.

The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber(A₀-1) thus produced contained ethylene at 68% by mol, and had anintrinsic viscosity [η] of 0.2 dl/g measured in decalin kept at 135° C.,iodine value (IV) of 10(g/100 g) and Mw/Mn of 15.

Two % toluene solution (0.3 g) of chloroplatinic acid and 1.5 g ofmethyldimethoxysilane were added to 100 g of theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A₀-1),and they were allowed to react with each other at 120° C. for 2 hours.The excess methyldimethoxysilane and the solvent (toluene) weredistilled off from the effluent. This produced 101.5 g of theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1)containing dimethoxymethylsilyl group (—SiCH₃(OCH₃)₂)

Production Example K2

[Production of the Saturated Hydrocarbon-based Polymer]

p-DCC, 7.5 mmols, represented by the following formula, compound A, wascharged in a 1 L pressure-resistant glass autoclave, to which agitatorblades, a 3-way cock and vacuum line were attached. Then, the autoclavewas purged by nitrogen.

Then, the autoclave was charged with 330 mL of toluene and 141 mL ofhexane, dried by a molecular sieve, as the solvents by a syringe, andthen with 3.0 mmols of α-picoline, while supplying nitrogen through oneside of the 3-way cock.

Next, a pressure-resistant glass-made liquefied gas collecting tubeequipped with a needle valve and containing 113 g of isobutylene, passedthrough a column packed with barium oxide for dehydration, was connectedto the 3-way cock. Then the autoclave as the polymerization reactor wasimmersed in a dry ice/acetone bath kept at −70° C., to cool the solutionfor 1 hour while stirring inside. The polymerization reactor wasevacuated to a vacuum via the vacuum line, after it was cooled, andcharged with isobutylene from the liquefied gas collecting tube byopening the needle valve. Then, the reactor inside was returned back tothe normal pressure by introducing nitrogen with handling the 3-waycock.

TiCl₄, 7.18 g (3.8 mmols) was charged in the polymerization reactor by asyringe via the 3-way cock, after confirming that the reactor inside waskept at −70° C., to initiate the polymerization. After a lapse of 2hours, 2.57 g (22.5 mmols) of allyl trimethylsilane was added to thereactor. The reaction process was continued for another 1 hour, andwater was added to the reaction mixture to deactivate the catalyst.Then, the organic layer was washed with pure water 3 times, and, afterwater was removed, distilled to remove the solvent under a vacuum. Thisproduced the isobutylene polymer with the allyl group at the terminal.

Compound A is represented by the following structural formula:

Then, 100 g of the isobutylene polymer with the allyl group at theterminal was dissolved in 50 mL of n-heptane, and the solution washeated to around70° C., to which1.2 [eq./allyl group] of methyldimethoxysilane and 1×10⁻⁴ [eq./allyl group] of platinum (vinylsiloxane) complex were added for the hydrosilylation. The reactionprocess was followed by FT-IR, and stopped in around 4 hours, afterconfirming that the olefin-derived absorption at 1640 cm⁻¹ disappeared.

The reaction solution was enriched under a vacuum, to produce theisobutylene polymer with the reactive silicon at both terminals,represented by the following formula:

The polymer yield was estimated from the quantity produced. It was alsoanalyzed for number-average molecular weight (Mn) and Mw/Mn by GPC, andthe terminal structure by comparing the intensities of the¹H-NMR-analyzed resonance signals of proton relevant to each structure(proton derived from the initiator: 6.5 to 7. 5 ppm, methyl protonbonded to the silicon atom, derived from the polymer terminal: 0.0 to0.1 ppm, and methoxy proton: 3.5 to 3.4) with each other. The polymerhad an Mn of 11,416, Mn/Mw of 1.47 and Fn (silyl) of 1.95(number-average molecular weight is a relative value to that of thestandard polystyrene, and Fn (silyl) is number of the terminalfunctional silyl groups in one molecule of the isobutylene polymer).

Example K1

A mixture containing the silyl-containingethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1),prepared in PRODUCTION EXAMPLE K1 , was prepared. It was composed of 100parts of the copolymer rubber (A-1), 90 parts of a paraffin-basedprocess oil (Idemitsu Kosan, Diana Process Oil PS-32™), 180 parts oflimestone powder (Shiraishi Calcium, PO320B™), 50 parts of colloidalcalcium carbonate (Shiraishi K. K., EDS-D10A™), 100 parts of talc (MaruoCalcium, LMR™), 1 part of an aging inhibitor (Ciba-Geigy Japan, Irganox1010™) as Aging Inhibitor 1, 1 part of another aging inhibitor (SumitomoChemical, Sumisorb 400™) as Aging Inhibitor 2, 1 part of still anotheraging inhibitor (Sankyo, Sanol LS-765™) as Aging Inhibitor 3, 3 parts ofa light stabilizer (Sanshin Kagaku Kogyo, Sandant NBC™), 3 parts oflight-curable resin (TOAGOSEI, Aronix M-400™), 5 parts of a thixotropyimparting agent (Kusumoto Kasei, Disparlon #305™), and 4 parts ofγ-isocyanate propyltriethoxysilane as the silane coupling agent (NipponUnicar, Y-9030™), all parts by weight. The mixture was well kneaded by a3-paint roll unit, to produce the major ingredient for REFERENCE EXAMPLEK1.

The curing agent was prepared for EXAMPLE K1 by the following procedure:a mixture comprising 4 parts of dibutyl tin bisacetylacetonate (NITTOKASEI, U-220™) as the silanol condensing catalyst, 4parts of salt cake(Na₂SO₄.10H₂O), 10 parts of a paraffin-based process oil (IdemitsuKosan, Diana Process Oil PS-32™), 20 parts of limestone powder (MaruoCalcium, Snowlite SS™), and 2.5 parts of carbon black (MitsubishiChemical, CB#30™), all parts by weight, was manually kneaded in adisposal cup and stirred 3 times at 10,000 rpm each for 10 minutes by ahomogenizer (Nihon Seiki Sesakusho Co., Ltd. Excel Auto Homogenizer).

The above composition put in a sealed glass bottle was stored for amonth in a perfect oven kept at 50° C., to measure viscosity of themajor ingredient.

The viscosity was measured by a B type viscometer (Tokyo Keiki, ModelBS) at 23° C. using a No. 7 rotor.

It had a viscosity of 8,525 poise at 10 rpm immediately after it wasprepared, and 9,020 poise also at 10 rpm after it was stored.

Reference Examples K1and K2

A mixture containing the polymer prepared in PRODUCTION EXAMPLE K2 wasprepared for each of REFERENCE EXAMPLES K1 and K2. It was composed of100 parts of the polymer, 90 parts of a paraffin-based process oil(Idemitsu Kosan, Diana Process Oil PS-32™), 180 parts of limestonepowder (Shiraishi Calcium, PO320B™), 50 parts of colloidal calciumcarbonate (Shiraishi K. K., EDS-D10A™), 100 parts of talc (MaruoCalcium, LMR™), 1 part of an aging inhibitor (Ciba-Geigy Japan, Irganox1010™) as Aging Inhibitor 1, 1 part of another aging inhibitor (SumitomoChemical, Sumisorb 400™) as Aging Inhibitor 2, 1 part of still anotheraging inhibitor (Sankyo, Sanol LS-765™) as Aging Inhibitor 3, 3 parts ofa light stabilizer (Sanshin Kagaku Kogyo, Sandant NBC™), 3 parts oflight-curable resin (TOAGOSEI, Aronix M-400™), 5 parts of a thixotropyimparting agent (Kusumoto Kasei, Disparlon #305™), and 4 parts ofγ-isocyanate propyltriethoxysilane as the silane coupling agent (NipponUnicar, Y-9030™), all parts by weight. The mixture was well kneaded by a3-paint roll unit, to produce the major ingredient for REFERENCE EXAMPLEK1.

The curing agent was prepared for REFERENCE EXAMPLE K1 by the followingprocedure: a mixture comprising 4 parts of dibutyl tinbisacetylacetonate (NITTO KASEI, U-220™) as the silanol condensingcatalyst, 4 parts of salt cake (Na₂SO₄.10H₂O), 10 parts of aparaffin-based process oil (Idemitsu Kosan, Diana Process Oil PS-32™),20 parts of limestone powder (Maruo Calcium, Snowlite SS™), and 2.5parts of carbon black (Mitsubishi Chemical, CB#30™), all parts byweight, was manually kneaded in a disposal cup and stirred 3 times at10,000 rpm each for 10 minutes by a homogenizer (Nihon Seiki SesakushoCo., Ltd. Excel Auto Homogenizer).

The major ingredient and curing agent were prepared for REFERENCEEXAMPLE K2 in the same manner as in REFERENCE EXAMPLE K1, except that 4parts of salt cake (Na₂SO₄.10H₂O) was incorporated in the former andomitted from the latter, to prepare the composition to be tested in thesame manner.

Each of the above compositions put in a sealed glass bottle was storedfor a month in a perfect oven kept at 50° C., to measure viscosity ofthe major ingredient.

The viscosity was measured by a B type viscometer (Tokyo Keiki, ModelBS) at 23° C. using a No. 7 rotor.

These compositions had a viscosity of 7,632 poise (REFERENCE EXAMPLE K1)and 8,928 poise (REFERENCE EXAMPLE K2) at 10 rpm immediately after theywere prepared, and 9,072 poise and higher than 12,000 poise (beyond themeasurable range), respectively, also at 10 rpm after they were stored.The results indicate that the major ingredient has a higher viscositywhen incorporated with a hydrate of metallic salt than when not, andthat its viscosity increases when it is stored.

Example K2

A mixture containing the ethylene/propylene/5-vinyl-2-norbornene randomcopolymer rubber (A-1), prepared in PRODUCTION EXAMPLE K1, was prepared.It was composed of 100 parts of the copolymer rubber (A-1), 90 parts ofa paraffin-based process oil (Idemitsu Kosan, Diana Process Oil PS-32™),180 parts of limestone powder (Shiraishi Calcium, PO320™) 50 parts ofcolloidal calcium carbonate (Shiraishi K. K., EDS-D10A™), 100 parts oftalc (Maruo Calcium, LMR™), 1 part of an aging inhibitor (Ciba-GeigyJapan, Irganox 1010™) as Aging Inhibitor 1, 1 part of another aginginhibitor (Sumitomo Chemical, Sumisorb 400™) as Aging Inhibitor 2, 1part of still another aging inhibitor (Sankyo, Sanol LS-765™) as AgingInhibitor 3, 3 parts of a light stabilizer (Sanshin Kagaku Kogyo,Sandant NBC™), 3 parts of light-curable resin (TOAGOSEI, Aronix M-400™),5 parts of a thixotropy imparting agent (Kusumoto Kasei, Disparlon#305™), 4 parts of γ-isocyanatepropyltriethoxysilane as the silanecoupling agent (Nippon Unicar, Y-9030™) and 2 parts ofγ-glycidoxypropyltrimethoxysilane (Nippon Unicar, A-187™), all parts byweight. The mixture was well kneaded by a 3-paint roll unit, to producethe major ingredient for REFERENCE EXAMPLE K2.

The curing agent was prepared for EXAMPLE K2 by the following procedure:a mixture comprising 4 parts of dibutyl tin bisacetylacetonate (NITTOKASEI, U-220™) as the silanol condensing catalyst, 4 parts of salt cake(Na₂SO₄.10H₂O), 10 parts of a paraffin-based process oil (IdemitsuKosan, Diana Process Oil PS-32™), 20 parts of limestone powder (MaruoCalcium, Snowlite SS™), and 2.5 parts of carbon black (MitsubishiChemical, CB#30™), all parts by weight, was manually kneaded in adisposal cup and stirred 3 times at 10,000 rpm each for 10 minutes by ahomogenizer (Nihon Seiki Sesakusho Co., Ltd. Excel Auto Homogenizer).

The above composition put in a sealed glass bottle was stored for amonth in a perfect oven kept at 50° C., to measure changes with time inadhesion to various base materials and mechanical characteristicsimmediately after it was prepared and after it was stored. The resultsare given in Tables K1 and K2.

The test piece for the tensile test was prepared in accordance with JISA-5758/1992 specifying the method for preparing the test piece for thetensile test; the composition comprising the major ingredient and curingagent in a given weight ratio was well kneaded and put in the H-shape ofglass or aluminum substrate, and cured in an oven.

The curing conditions were 23° C.×7 days+50° C.×7 days for eachcomposition.

Three types of materials were used to prepare substrates for the H-typetensile test; float glass (Koen-sha, designated by Japan SealantIndustry Association, 3 by 5 by 0.5 cm in size) in accordance with JISA-5758/1992, pure aluminum (Taiyu Kizai, A1100P, 5 by 5 by 0.2 cm insize) in accordance with JIS H-4000, and heat ray reflective glass(KLS™, 5 by 5 by 0.6 cm). Each of these H-shapes was washed withmethylethylketone (Wako-Junyaku Kogyo, special grade) and wiped withclean cotton cloth, before it was filled with the composition.

The H-shape test piece thus prepared was tested by the method of testingtensile adhesion in accordance with JIS A-5758/1992, wherein it wascured at a tensile speed of 50 mm/minute in a constant-temperaturechamber kept at 23° C. and 65±5% RH. The cohesion fracture (CF)/thinfilm fracture (TCF)/adhesion fracture (AF) ratio shown in the tables forthe K Series were determined by visual observation of the cross-sectionsof the tensile-tested pieces.

Reference Examples K3 and K4

A mixture containing the polymer prepared in PRODUCTION EXAMPLE K2 wasprepared for each of REFERENCE EXAMPLES K3 and K4. It was composed of100 parts of the polymer, 90 parts of a paraffin-based process oil(Idemitsu Kosan, Diana Process Oil PS-32™), 180 parts of limestonepowder (Shiraishi Calcium, PO320B™), 50 parts of colloidal calciumcarbonate (Shiraishi K. K., EDS-D10A™), 100 parts of talc (MaruoCalcium, LMR™), 1 part of an aging inhibitor (Ciba-Geigy Japan, Irganox1010™) as Aging Inhibitor 1, 1 part of another aging inhibitor (SumitomoChemical, Sumisorb 400™) as Aging Inhibitor 2, 1 part of still anotheraging inhibitor (Sankyo, Sanol LS-765™) as Aging Inhibitor 3, 3 parts ofa light stabilizer (Sanshin Kagaku Kogyo, Sandant NBC™), 3 parts oflight-curable resin (TOAGOSEI, Aronix M-400™), 5 parts of a thixotropyimparting agent (Kusumoto Kasei, Disparlon #305™), 4 parts ofγ-isocyanate propyltriethoxysilane as the silane coupling agent (NipponUnicar, Y-9030™), and 2 parts of γ-glycidoxypropyltrimethoxysilane(Nippon Unicar, A-187™), all parts by weight. The mixture was wellkneaded by a 3-paint roll unit, to produce the major ingredient forREFERENCE EXAMPLE K3.

The curing agent was prepared for REFERENCE EXAMPLE K3 by the followingprocedure: a mixture comprising 4 parts of dibutyl tinbisacetylacetonate (NITTO KASEI, U-220™) as the silanol condensingcatalyst, 4 parts of salt cake (Na₂SO₄.10H₂O), 10 parts of aparaffin-based process oil (Idemitsu Kosan, Diana Process Oil PS-32™),20 parts of limestone powder (Maruo Calcium, Snowlite SS™), and 2.5parts of carbon black (Mitsubishi Chemical, CB#30™), all parts byweight, was manually kneaded in a disposal cup and stirred 3 times at10,000 rpm each for 10 minutes by a homogenizer (Nihon Seiki SesakushoCo., Ltd. Excel Auto Homogenizer).

The major ingredient and curing agent were prepared for REFERENCEEXAMPLE K4 in the same manner as in REFERENCE EXAMPLE K3, except that 4parts of salt cake (Na₂SO₄.10H₂O) was incorporated in the majoringredient of REFERENCE EXAMPLE K3 and omitted from the curing agent ofREFERENCE EXAMPLE K3, to prepare the composition to be tested in thesame manner.

Each of the above compositions put in a sealed glass bottle was storedfor a month in a perfect oven kept at 50° C., to measure changes withtime in adhesion to various base materials and mechanicalcharacteristics immediately after it was prepared and after it wasstored. The results are given in Tables K1 and K2.

The test piece for the tensile test was prepared in accordance with JISA-5758/1992 specifying the method for preparing the test piece for thetensile test; the composition comprising the major ingredient and curingagent in a given ratio was well kneaded and put in the H-shape of glassor aluminum substrate, and cured in an oven.

The curing conditions were 23° C.×7 days+50° C.×7 days for eachcomposition.

Three types of materials were used to prepare substrates for the H-typetensile test; float glass (Koen-sha, designated by Japan SealantIndustry Association, 3 by 5 by 0.5 cm in size) in accordance with JISA-5758/1992, pure aluminum (Taiyu Kizai, A1100P, 5 by 5 by 0.2 cm insize) in accordance with JIS H-4000, and heat ray reflective glass(KLS™, 5 by 5 by 0.6 cm in size) Each of these H-shapes was washed withmethylethylketone (Wako-Junyaku Kogyo, special grade) and wiped withclean cotton cloth, before it was filled with the composition.

The H-shape test piece thus prepared was tested by the method of testingtensile adhesion in accordance with JIS A-5758/1992, wherein it wascured at a tensile speed of 50 mm/minute in a constant-temperaturechamber kept at 23° C. and 65±5% RH. The cohesion fracture (CF)/thinfilm fracture (TCF)/adhesion fracture (AF) ratio shown in the tables forthe K Series were determined by visual observation of the cross-sectionsof the tensile-tested pieces.

TABLE K1 (H type tensile test results with the just producedcompositions) M₅₀ T_(B) Fractured conditions kgf/ kgf/ E_(B) (%)Substrate cm² cm² % CF TCF AF EXAMPLE K2 FL 6.22 6.60 68 100 0 0 pAl5.10 6.80 72 100 0 0 KLS 5.20 6.61 68 100 0 0 REFERENCE FL 6.14 7.80 79100 0 0 EXAMPLE K3 pAl 5.56 7.96 88 100 0 0 KLS 5.97 7.79 82 99 1 0REFERENCE FL 5.48 7.49 85 99 1 0 EXAMPLE K4 pAl 4.94 8.13 107 94 5 1 KLS5.39 7.82 95 99 1 0 (Notes) FL: Float glass, pAl: pure aluminum, KLS:Heat ray reflective glass, M₅₀: 50% Tensile stress, T_(B): Tensilebreaking strength, E_(B): Tensile breaking elongation

TABLE K2 (H type tensile test results with the stored compositions) M₅₀T_(B) kgf/ kgf/ E_(B) Fractured conditions (%) Substrate cm² cm² % CFTCF AF EXAMPLE K2 FL 5.20 7.10 79 100 0 0 pAl 5.12 7.32 85 98 2 0 KLS5.24 7.06 77 98 2 0 REFERENCE FL 5.94 8.88 91 100 0 0 EXAMPLE K3 pAl5.47 8.39 93 97 0 3 KLS 6.50 9.01 81 98 2 0 REFERENCE FL — 2.62 30 1 099 EXAMPLE K4 pAl — 1.85 23 0 0 100 KLS — 1.32 15 0 0 100 (Notes) FL:Float glass, pAl: pure aluminum, KLS: Heat ray reflective glass, M₅₀:50% Tensile stress, T_(B): Tensile breaking strength, E_(B): Tensilebreaking elongation

Example K3

The curing agent was prepared in the same manner as in EXAMPLE K2,except that U-220 as the silanol condensing catalyst was replaced by 4parts by weight of dibutyl tin dimethoxide (Aldrich Chemical), andtested also by use of the major ingredient of EXAMPLE K2 in the samemanner as in EXAMPLE K2. The results are given in Tables K3 and K4.

Reference Example K5

The curing agent was prepared in the same manner as in REFERENCE EXAMPLEK3, except that U-220 as the silanol condensing catalyst was replaced by4 parts by weight of dibutyl tin dimethoxide (Aldrich Chemical), andtested also by use of the major ingredient of REFERENCE EXAMPLE K3 inthe same manner as in REFERENCE EXAMPLE K3. The results are given inTables K3 and K4.

TABLE K3 (H type tensile test results with the just producedcompositions) M₅₀ T_(B) Fractured conditions kgf/ kgf/ E_(B) (%)Substrate cm² cm² % CF TCF AF EXAMPLE K3 FL 3.78 6.53 113 100 0 0 pAl3.69 6.70 120 98 2 0 KLS 3.82 6.74 122 98 2 0 REFERENCE FL 4.42 7.70 130100 0 0 EXAMPLE K5 pAl 4.23 8.32 144 97 3 0 KLS 4.60 7.26 127 97 3 0(Notes) FL: Float glass, pAl: pure aluminum, KLS: Heat ray reflectiveglass, M₅₀: 50% Tensile stress, T_(B): Tensile breaking strength, E_(B):Tensile breaking elongation

TABLE K4 (H type tensile test results with the stored compositions) M₅₀T_(B) Fractured conditions kgf/ kgf/ E_(B) (%) Substrate cm² cm² % CFTCF AF EXAMPLE K3 FL 3.86 7.09 116 100 0 0 pAl 3.76 7.22 122 99 1 0 KLS3.86 7.33 126 100 0 0 REFERENCE FL 4.50 8.34 133 98 0 2 EXAMPLE K5 pAl4.32 8.46 139 100 0 0 KLS 4.69 8.41 125 100 0 0 (Notes) FL: Float glass,pAl = pure aluminium, KLS: Heat ray reflective glass, M₅₀: 50% Tensilestress, T_(B): Tensile breaking strength, E_(B): Tensile breakingelongation

Examples K4 to K7

A mixture containing the silyl-containingethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1),prepared in PRODUCTION EXAMPLE K1, was prepared for each of EXAMPLES K4to K7. It was composed of 100 parts of the copolymer rubber (A-1), 90parts of a paraffin-based process oil (Idemitsu Kosan, Diana Process OilPS-32™), 180 parts of limestone powder (Shiraishi Calcium, PO320B™), 50parts of colloidal calcium carbonate (Shiraishi K. K., EDS-D10A™), 100parts of talc (Maruo Calcium, LMR™), 1 part of an aging inhibitor(Ciba-Geigy Japan, Irganox 1010™) as Aging Inhibitor 1, 1 part ofanother aging inhibitor (Sumitomo Chemical, Sumisorb 400™) as AgingInhibitor 2, 1 part of still another aging inhibitor (Sankyo, SanolLS-765™) as Aging Inhibitor 3, 3 parts of a light stabilizer (SanshinKagaku Kogyo, Sandant NBC™), 5 parts of a thixotropy imparting agent(Kusumoto Kasei, Disparlon#305™), 4 parts of the silane coupling agent 1(Nippon Unicar, Y-9030™) and 2 parts of the silane coupling agent 2(Nippon Unicar, A-187™), all parts by weight. The mixture was wellkneaded by a 3-paint roll unit, to produce the major ingredient forREFERENCE EXAMPLES K6 to K9.

The curing agent was prepared for EXAMPLE K4 by the following procedure:a mixture comprising 4 parts of the silanol condensing catalyst (NITTOKASEI, U-220™), 4 parts of salt cake (Na₂SO₄.10H₂O), 10 parts of aparaffin-based process oil (Idemitsu Kosan, Diana Process Oil PS-32™),20 parts of limestone powder (Maruo Calcium, Snowlite SS™), and 2.5parts of carbon black (Mitsubishi Chemical, CB#30™), all parts byweight, was manually kneaded in a disposal cup and stirred 3 times at10,000 rpm each for 10 minutes by a homogenizer (Nihon Seiki SesakushoCo., Ltd. Excel Auto Homogenizer).

The composition was prepared for each of EXAMPLES K4 to K7 in the samemanner as in EXAMPLE K2, except that salt cake (Na₂SO₄.10H₂O) for thecuring agent was replaced by another hydrate of metallic salt, 6 partsof hypo (Na₂S₂O₃.5H₂O) for EXAMPLE K5, 6 parts of magnesium sulfate(MgSO₄.7H₂O) for EXAMPLE K6 and 4 parts of sodium phosphate(Na₃PO₄.12H₂O) for EXAMPLE K7 to prepare the curing agent, and tested inthe same manner as in EXAMPLE K2. The results are given in Tables K5 andK6.

Reference Examples K6 to K9

A mixture containing the polymer prepared in PRODUCTION EXAMPLE K2 wasprepared for each of REFERENCE EXAMPLES K6 to K9. It was composed of 100parts of the polymer, 90 parts of a paraffin-based process oil (IdemitsuKosan, Diana Process Oil PS-32™), 180 parts of limestone powder(Shiraishi Calcium, PO320B™), 50 parts of colloidal calcium carbonate(Shiraishi K. K., EDS-D10A™), 100 parts of talc (Maruo Calcium, LMR™), 1part of an aging inhibitor (Ciba-Geigy Japan, Irganox 1010™) as AgingInhibitor 1, 1 part of another aging inhibitor (Sumitomo Chemical,Sumisorb 400™) as Aging Inhibitor 2, 1 part of still another aginginhibitor (Sankyo, Sanol LS-765™) as Aging Inhibitor 3, 3 parts of alight stabilizer (Sanshin Kagaku Kogyo, Sandant NBC™), 5 parts of athixotropy imparting agent (Kusumoto Kasei, Disparlon #305™), 4 parts ofsilane coupling agent 1 (Nippon Unicar, Y-9030™) and 2 parts of silanecoupling agent 2 (Nippon Unicar, A-187™), all parts by weight. Themixture was well kneaded by a 3-paint roll unit, to produce the majoringredient.

The curing agent was prepared for REFERENCE EXAMPLE K6 by the followingprocedure: a mixture comprising 4 parts of the silanol condensingcatalyst (NITTO KASEI, U-220™), 4 parts of salt cake (Na₂SO₄.10H₂O), 10parts of a paraffin-based process oil (Idemitsu Kosan, Diana Process OilPS-32™), 20 parts of limestone powder (Maruo Calcium, Snowlite SS™), and2.5 parts of carbon black (Mitsubishi Chemical, CB#30™), all parts byweight, was manually kneaded in a disposal cup and stirred 3 times at10,000 rpm each for 10 minutes by a homogenizer (Nihon Seiki SeisakushoCo., Ltd. Excel Auto Homogenizer).

The composition was prepared for each of REFERENCE EXAMPLES K7 to K9 inthe same manner as in REFERENCE EXAMPLE K3, except that salt cake(Na₂SO₄.10H₂O) for the curing agent was replaced by another hydrate ofmetallic salt, 6 parts of hypo (Na₂S₂O₃.5H₂O) for REFERENCE EXAMPLE K7,6 parts of magnesium sulfate (MgSO₄.7H₂O) for REFERENCE EXAMPLE K8 and 4parts of sodium phosphate (Na₃PO₄.12H₂O) for REFERENCE EXAMPLE K9 toprepare the curing agent, and tested in the same manner as in REFERENCEEXAMPLE K3. The results are given in Tables K5 and K6.

The composition comprising the major ingredient and curing agent,prepared in each of EXAMPLES K1 to K7 and REFERENCE EXAMPLES K1 to K9was tested for curing speed and resistance to weather by the methodsdescribed earlier.

The results are given in Table K7.

TABLE K5 (H type tensile test results with the just producedcompositions) M₅₀ T_(B) Fractured conditions kgf/ kgf/ E_(B) (%)Substrate cm² cm² % CF TCF AF EXAMPLE K4 FL 4.32 5.94 83 100 0 0 KLS4.36 5.80 78 100 0 0 EXAMPLE K5 FL 4.85 6.20 72 100 0 0 KLS 4.90 6.04 68100 0 0 EXAMPLE K6 FL 4.59 6.80 88 100 0 0 KLS 4.60 6.62 83 100 0 0EXAMPLE K7 FL 4.18 6.20 91 100 0 0 KLS 4.23 6.00 86 100 0 0 REFERENCE FL4.92 7.40 94 100 0 0 EXAMPLE K6 KLS 5.20 7.29 83 99 1 0 REFERENCE FL5.51 7.71 80 100 0 0 EXAMPLE K7 KLS 5.63 7.45 74 100 0 0 REFERENCE FL5.22 8.45 99 100 0 0 EXAMPLE K8 KLS 5.31 7.94 87 100 0 0 REFERENCE FL4.78 7.69 102 100 0 0 EXAMPLE K9 KLS 5.12 7.76 96 100 0 0 (Notes) FL:Float glass, KLS: Heat ray reflective glass, M₅₀: 50% Tensile stress,T_(B): Tensile breaking strength, E_(B): Tensile breaking elongation

TABLE K6 (H type tensile test results with the stores compositions) M₅₀T_(B) Fractured conditions kgf/ kgf/ E_(B) (%) Substrate cm² cm² % CFTCF AF EXAMPLE K4 FL 4.33 6.25 84 100 0 0 KLS 4.34 6.34 91 100 0 0EXAMPLE K5 FL 4.87 6.70 80 100 0 0 KLS 4.88 6.80 77 100 0 0 EXAMPLE K6FL 4.58 7.00 92 100 0 0 KLS 4.54 7.42 94 100 0 0 EXAMPLE K7 FL 4.22 6.8095 100 0 0 KLS 4.32 6.90 102 100 0 0 REFERENCE FL 4.92 7.40 90 100 0 0EXAMPLE K6 KLS 5.20 7.29 83 99 1 0 REFERENCE FL 5.51 7.71 80 100 0 0EXAMPLE K7 KLS 5.63 7.45 74 100 0 0 REFERENCE FL 5.22 8.45 99 100 0 0EXAMPLE K8 KLS 5.31 7.94 87 100 0 0 REFERENCE FL 4.78 7.69 102 100 0 0EXAMPLE K9 KLS 5.12 7.76 96 100 0 0 (Notes) FL: Float glass, KLS: Heatray reflective glass, M₅₀: 50% Tensile stress, T_(B): Tensile breakingstrength, E_(B): Tensile breaking elongation

TABLE K7 Just produced compositions Stored compositions Curing speedResistance to weather Curing speed Resistance to weather EXAMPLE K1 ∘ Nocracks or molten ∘ No cracks or molten portion observed portion observedREFERENCE x No cracks or molten x No cracks or molten EXAMPLE K1 portionobserved portion observed REFERENCE x No cracks or molten x No cracks ormolten EXAMPLE K2 portion observed portion observed EXAMPLE K2 ∘ Nocracks or molten ∘ No cracks or molten portion observed portion observedREFERENCE x No cracks or molten x No cracks or molten EXAMPLE K3 portionobserved portion observed REFERENCE x No cracks or molten x No cracks ormolten EXAMPLE K4 portion observed portion observed EXAMPLE K3 ∘ Nocracks or molten ∘ No cracks or molten portion observed portion observedREFERENCE x No cracks or molten x No cracks or molten EXAMPLE K5 portionobserved portion observed EXAMPLE K4 ∘ No cracks or molten ∘ No cracksor molten portion observed portion observed EXAMPLE K5 ∘ No cracks ormolten ∘ No cracks or molten portion observed portion observed EXAMPLEK6 ∘ No cracks or molten ∘ No cracks or molten portion observed portionobserved EXAMPLE K7 ∘ No cracks or molten ∘ No cracks or molten portionobserved portion observed REFERENCE x No cracks or molten x No cracks ormolten EXAMPLE K6 portion observed portion observed REFERENCE x Nocracks or molten x No cracks or molten EXAMPLE K7 portion observedportion observed REFERENCE x No cracks or molten x No cracks or moltenEXAMPLE K8 portion observed portion observed REFERENCE x No cracks ormolten x No cracks or molten EXAMPLE K9 portion observed portionobserved

Examples L Series Production Example 1

[Production of Silyl-containing ethylene/propylene/5-vinyl-2-norborneneRandom Copolymer Rubber]

The three-component copolymerization was effected continuously in astainless steel polymerization reactor having an essential capacity of100 L, equipped with agitator blades (agitating rotation speed: 250rpm), wherein hexane, ethylene, propylene and 5-vinyl-2-norbornene werecontinuously supplied at 60 L, 2.5 kg, 4.0 kg and 380 g per hour,respectively, from the reactor side into the liquid phase, and hydrogen,VO(OC₂H₅)₂Cl and Al(Et)_(1.5)Cl_(1.5) as the catalysts at 700 L, 45mmols and 315 mmols per hour, respectively also continuously.

The copolymerization effected under the above conditions produced theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber in aform of uniform solution.

A small quantity of methanol was added to the polymer solution,continuously withdrawn from the reactor bottom, to terminate thepolymerization. The polymer was separated from the solvent bysteam-stripping the solution, and dried at 55° C. for 48 hours under avacuum.

The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber thusproduced contained ethylene at 68% by mol, and had an iodine value of10, an intrinsic viscosity [η] of 0.2 dl/g, and Mw/Mn of 15.

Two % toluene solution (0.3 g) of chloroplatinic acid and 1.5 g ofmethyldimethoxysilane were added to 100 g of theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber, andthey were allowed to react with each other at 120° C. for 2 hours. Theexcess methyldimethoxysilane and the solvent were distilled off from theeffluent. This produced 101.5 g of the copolymer rubber containingdimethoxymethylsilyl group.

Examples L1 to L4, and Comparative Example L1

A uniform rubber composition was prepared in each of EXAMPLES L1 to L4,and COMPARATIVE EXAMPLE L1 using the components given in Table L1 in aratio also given in Table L1, to measure its viscosity. The results areshown in Table L1.

Each composition prepared was flow-cast to a 3 mm thick sheet, and curedat room temperature for 4 days and 50° C. for another 4 days.

The cured sheet was evaluated for its tackiness, resistance to heat,curing speed and resistance to weather by the following methods.

Curing speed (film expandability) and resistance to weather were alsomeasured using different aliquots of each example. The results are givenin Table L2.

1) Tackiness

Tackiness was evaluated according to the following three-grade system byfeeling of touching the sheet with a finger:

-   ⊚: No tackiness is felt to the touch-   ◯: Tackiness is felt to the touch slightly-   Δ: Tackiness is felt to the touch    2) Resistance to Heat

Resistance to heat was evaluated by the time required for the sheetsurface to start melting at 130° C.

3) Resistance to Weather

Resistance to weather was evaluated by the time required for the sheetsurface to start melting in the accelerated weather resistance testusing a Sunshine weatherometer.

4) Curing Speed Test

The composition comprising the major ingredient and the catalyst wasmeasured for its film expandability at room temperature, i.e., curingspeed.

The composition and mold (20 by 80 by 5 mm in size) were kept andadjusted under the conditions of 23° C. and 50% RH overnight, and thenthe mold was filled with the composition. Next, the cured compositionwas released from the mold after it was kept therein for 24 hours, andthickness of the cured portion was measured by a dial gauge of weakspring force to 0.1 mm, to evaluate its curing speed.

(Evaluation Standards)

-   -   ×: when thickness of the cured portion is less than 1 mm    -   ◯: when thickness of the cured portion is 1 mm or more        5) Weather Resistance Test

The accelerated weather resistance test was conducted in accordance withJIS B-7753:

-   Analyzer: Sunshine Carbon Arc weatherometer-   Light irradiation/rainfall cycles: Irradiation for 120    minutes/rainfall for 18 minutes-   Black panel temperature: 63±2° C.-   Tank inside temperature: 40±2° C.-   Total light irradiation time: 500 hours

The surface state of tested test piece was visually observed, toevaluate its resistance to weather according to the following threegrades:

-   ◯: No cracks or molten portion observed-   Δ: Cracks or molten portion observed slightly-   ×: Cracks or molten portion observed

Reference Examples L1 to L6

Three types of polymers containing a reactive silicon group wereprepared by the methods disclosed by Japanese Patent Laid-OpenPublication No. 252670/1989 in PRODUCTION EXAMPLES 1 to 3 (column 16 to18).

A uniform rubber composition was prepared using each of these polymersand other components shown in Tale L1. Table L1 describes the ratio ofthese compositions.

These rubber compositions and those cured products prepared in EXAMPLESwere evaluated for the properties in the same manner as in EXAMPLES. Theresults are given in Table L1.

TABLE L1 Composition REFERENCE REFERENCE REFERENCE REFERENCE COMPARATIVEREFERENCE REFERENCE (Parts) EXAMPLE L1 EXAMPLE L2 EXAMPLE L1 EXAMPLE L2EXAMPLE L3 EXAMPLE L4 EXAMPLE L3 EXAMPLE L4 EXAMPLE L1 EXAMPLE L5EXAMPLE L6 Component (A2) PRODUCTION 80 80 — — 100 100 — — 100 — —EXAMPLE L1 PRODUCTION — — 80 80 — — — — — 100 — EXAMPLE L2 (Note 6)PRODUCTION — — — — — — 100 100 — — 100 EXAMPLE L3 (Note 7) Component(K1) PS 340.5 (Note 1) 20 — 20 — — — — — — — — PS 084 (Note 2) — 20 — 20— — — — — — — PS 080 (Note 3) — — — — 24 (Note 4) 35 (Note 5) 80 (Note4) 90 (Note 5) — — — Tin octylate 3 3 3 3 3 3 3 3 3 3 3 Lauryl amine0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 Curability ◯ ◯ XX ◯ ◯ X X ◯ X X (day, 23° C.) Tackiness ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ◯ Δ ◯ Resistanceto 110 105 45 48 120 115 40 41 115 50 43 heat (day) Resistance to ◯ ◯ ΔΔ ◯ ◯ Δ Δ ◯ Δ Δ weather (day) Notes for Table L1: (Note 1) PS 340.5:Polydimethylsiloxane with a silanol group at the terminal (Chisso Corp.)(Note 2) PS 084: Polydimethyldiphenylsiloxane with a diphenyl silanolgroup at the terminal (Chisso Corp.) (Note 3) PS 080:Polydiphenylsiloxane with a silanol group at the terminal (Chisso Corp.)(Note 4) Ratio of silanol group in polysiloxane to methoxysilyl group inthe polymer: 1 by equivalent (Note 5) Ratio of silanol group inpolysiloxane to methoxysilyl group in the polymer: 1.2 by equivalent(Note 6) Polymer with a reactive silicon group, synthesized inaccordance with the methods disclosed by Japanese Patent Laid-OpenPublication No.252670/1989 in PRODUCTION EXAMPLE 1 (column 16 to 18).(Note 7) Polymer with a reactive silicon group, synthesized inaccordance with the methods disclosed by Japanese Patent Laid-OpenPublication No.252670/1989 in PRODUCTION EXAMPLE 3 (column 16 to 18).

Examples M Series Production Example M1

[Production of Silyl-containing ethylene/propylene/5-vinyl-2-norborneneRandom Copolymer Rubber]

The three-component copolymerization was effected continuously in astainless steel polymerization reactor having an essential capacity of100 L, equipped with agitator blades (agitating rotation speed: 250rpm), wherein hexane, ethylene, propylene and 5-vinyl-2-norbornene werecontinuously supplied at 60 L, 2.5 kg, 4.0 kg and 380 g per hour,respectively, from the reactor side into the liquid phase, and hydrogen,VO(OC₂H₅)₂Cl and Al(Et)_(1.5)C_(1.5) as the catalysts at 700 L, 45 mmolsand 315 mmols per hour, respectively also continuously.

The copolymerization effected under the above conditions produced theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber in aform of uniform solution.

A small quantity of methanol was added to the polymer solution,continuously withdrawn from the reactor bottom, to terminate thepolymerization. The polymer was separated from the solvent bysteam-stripping the solution, and dried at 55° C. for 48 hours under avacuum.

The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber thusproduced contained ethylene at 68% by mol, and had an iodine value of10, an intrinsic viscosity [η] of 0.2 dl/g, and Mw/Mn of 15.

Two % toluene solution (0.3 g) of chloroplatinic acid and 1.5 g ofmethyldimethoxysilane were added to 100 g of theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber, andthey were allowed to react with each other at 120° C. for 2 hours. Theexcess methyldimethoxysilane and the solvent were distilled off from theeffluent. This produced 101.5 g of the random copolymer rubbercontaining dimethoxymethylsilyl group.

Examples M1 to M5

A rubber composition was prepared in each of EXAMPLES M1 to M5 using thecomponents given in Table M1 in a ratio also given in Table M1. Itcomprised the dimethoxymethylsilyl group containing copolymer rubberprepared in PRODUCTION EXAMPLE M1 as the component (A2); and an organicrubber of polybutadiene rubber, stytrene/butadiene copolymer rubber,acrylic rubber (JSR Corp., AR101), polypropylene glycol containing ahydrolyzable silyl group (KANEKA CORP., MS Polymer, MS203™) or nitrilerubber (JSR Corp., N230S) as the component (K2). The mixture was kneadedby a Banbury mixer (Kobe Steel, Ltd. 1.9) at 120° C. for 5 minutes, andfurther by an 8-inch open roll in the presence of a vulcanizing agent.The sample of the rubber composition was measured for vulcanizing speedT₉₀ in accordance with JIS K-6300/1994.

Moreover, it was extruded into a sheet by a biaxial extruder, andcontinuously vulcanized under heating at 180° C. for 1 hour, to producethe vulcanized rubber sheet.

The cured sheet was evaluated for tensile elongation, resistance toheat, surface resistance to weather, curing speed and resistance toweather by the following methods. The results are given in Table M1.

(Evaluation Methods)

1) Tensile Test

The tensile test was conducted in accordance with JIS 6251 at 23° C.using the JIS No. 1 dumbbell-shaped test piece.

2) Weather Resistance Test

The accelerated weather resistance test was conducted in accordance withJIS B-7753, to determine resistance to weather:

-   Analyzer: Sunshine Carbon Arc weatherometer-   Light irradiation/rainfall cycles: Irradiation for 120    minutes/rainfall for 18 minutes-   Black panel temperature: 63±2° C.-   Tank inside temperature: 40±2° C.-   Total light irradiation time: 500 hours

The surface state of tested test piece was visually observed, toevaluate its resistance to weather according to the following threegrades:

-   ◯: No cracks or molten portion observed-   Δ: Cracks or molten portion observed slightly-   ×: Cracks or molten portion observed

Reference Examples M1 to M5

The vulcanized rubber sheet was prepared and tested in each of REFERENCEEXAMPLES M1 to M5 as shown in Table M1 in the same manner as incorresponding EXAMPLE, except that the silyl-containing copolymer rubberas the component (A2) was replaced by the compound A (represented by thefollowing general formula), synthesized by the method disclosed byJapanese Patent Laid-Open Publication No. 105005/1988, and having anumber-average molecular weight of 10, 600, a molecular weightdistribution (Mw/Mn) of 1.2 and terminal functional dimethoxymethylsilylgroup number of 1.9. The results are given in Table M1.

Compound A

wherein, “r” and “s” are each an integer.

TABLE M1 EXAMPLES REFERENCE EXAMPLES M1 M2 M3 M4 M5 M1 M2 M3 M4 M5Composition (parts by weight) Component (A2) Silyl-containing copolymerrubber compound A 50 50 50 50 50 Component (K2) Polybutadiene rubberStyrene/butadiene copolymer rubber 50 100 Acrylic rubber 50 100 MSPolymer, MS203 50 100 Nitrile rubber 50 100 Other component Asahi #60G50 100 Vulcanizer (M) 40 40 40 40 40 40 40 40 40 40 Dicumyl peroxide 2.72.7 2.7 2.7 2.7 2.7 2.7 2.7 2.7 2.7 Curing speed of rubber composition:T90 (170° C.) minutes Properties of the cured product 5.6 5.8 6.2 6.96.5 6.8 6.5 8.2 10.5 8.6 Tensile elongation (%) 400 420 480 500 490 250280 290 300 310 Resistance to weather ◯ ◯ ◯ ◯ ◯ Δ Δ Δ Δ Δ Notes) MSPolymer MS203 ™: Polypropylene glycol containing a hydrolysable silylgroup, KANEKA Corp. Asahi #60G: FEF grade carbon black, Asahi Carbon

As shown in Table M1, the rubber composition prepared in each ofEXAMPLES is superior to that prepared in corresponding REFERENCE EXAMPLEin all of curing speed, and surface resistance to weather, resistance toweather and resistance to heat in its cured product.

Examples N Series Production Example 1

[Production of Silyl-containing ethylene/propylene/5-vinyl-2-norborneneRandom Copolymer Rubber]

The three-component copolymerization was effected continuously in astainless steel polymerization reactor having an essential capacity of100 L, equipped with agitator blades (agitating rotation speed: 250rpm), wherein hexane, ethylene, propylene and 5-vinyl-2-norbornene werecontinuously supplied at 60 L, 2.5 kg, 4.0 kg and 380 g per hour,respectively, from the reactor side into the liquid phase, and hydrogen,VO(OC₂H₅)₂Cl and Al(Et)_(1.5)Cl_(1.5) as the catalysts at 700 L, 45mmols and 315 mmols per hour, respectively, also continuously.

The copolymerization effected under the above conditions produced theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber in aform of uniform solution.

A small quantity of methanol was added to the polymer solution,continuously withdrawn from the reactor bottom, to terminate thepolymerization. The polymer was separated from the solvent bysteam-stripping the solution, and dried at 55° C. for 48 hours under avacuum.

The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber thusproduced contained ethylene at 68% by mol, and had an iodine value of10, an intrinsic viscosity [η] of 0.2 dl/g, and Mw/Mn of 15.

Two % toluene solution (0.3 g) of chloroplatinic acid and 1.5 g ofmethyldimethoxysilane were added to 100 g of theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber, andthey were allowed to react with each other at 120° C. for 2 hours. Theexcess methyldimethoxysilane and the solvent were distilled off from theeffluent. This produced 101.5 g of the random copolymer rubbercontaining dimethoxymethylsilyl group.

Reference Production Examples 1 to 6

The polymer was prepared in each of REFERENCE PRODUCTION EXAMPLES 1 to 6in accordance with the respective method of PRODUCTION EXAMPLES 1 to 6disclosed by Japanese Patent Laid-Open Publication No. 292616/1992[0036] to [0037].

Examples N1 TO N4, and Reference Examples N1 to N6

The curable resin composition was prepared in each of EXAMPLES N1 to N4using the components given in Table N1 in a weight ratio also given inTable N1. It comprised the copolymer rubber containing dimethoxysilylgroup, prepared in PRODUCTION EXAMPLE 1, an epichlorohydrin-bisphenol Atype epoxy resin (Yuka Shell Epoxy, Epikote #828™, epoxy equivalents:around 190), γ-(2-aminoethyl)aminopropyl trimethoxysilane (NipponUnicar, A1122™) as the silane coupling agent, 50/50 mixture of dibutyltin oxide and dioctyl phthalate (Sankyo Organic Chemicals, Ltd., #918™)as the silanol condensing catalyst, and 2,4,6-tris(dimethylaminomethyl)phenol (Kayaku Nooly Co., Ltd., DMP30™) as theepoxy resin curing catalyst. The composition was also prepared in thesame manner as in the above, except that the polymers prepared inCOMPARATIVE PRODUCTION EXAMPLES 1 to 6 were used for respectiveCOMPARATIVE EXAMPLES N1 to N6.

The curable resin composition prepared in each of EXAMPLES N1 to N4, andCOMPARATIVE EXAMPLES N1 to N6 was evaluated by the following methods.

1) Tensile Test Using the Dumbbell-Shaped Test Piece

The curable resin composition was molded in a Teflon frame into a sheetby curing at 23° C. for 3 days and 50° C. for another 4 days. The curedsheet was stamped out into the No. 3 dumbbell-shaped test piece inaccordance with JIS K-6301. It was stretched at 200 mm/minute, todetermine its moduli at 50 and 100% tension (M₅₀ and M₁₀₀), breakingstrength (T_(B)) and breaking elongation (E_(B)).

2) Measurement of Tensile Shear Strength

The test was conducted in accordance with JIS K-6850. An aluminum plate(A-1050P aluminum plate, 100 by 25 by 2 mm in size, specified byJISH-4000) was wiped lightly with acetone, on which the curable resincomposition was spread by a spatula to an area of around 25 by 12.5 mmand thickness of 0.05 mm. The coated surfaces of the two plates wereattached face-to-face and manually pressed against each other. Thecoated test pieces were fixed, and the resin was cured at 23° C. for 3days and 50° C. for another 4 days. Then, they were stretched at 5mm/minute away from each other until their cured resin was fractured.The maximum load value measured at which the cured resin was fracturedwas divided by the coated area to find the tensile shear strength.

Curing speed and resistance to weather were measured by the followingmethods:

3) Curing Speed

The composition comprising the major ingredient and the catalyst wasmeasured for its film expandability at room temperature, i.e., curingspeed.

The curable composition was cured at 23° C. and 50% RH for 24 hours in amold (20 by 80 by 5 mm in size), and thickness of the cured portion wasmeasured by a dial gauge of weak spring force to 0.1 mm.

(Evaluation Standards)

-   -   ×: when thickness of the cured portion is less than 1 mm    -   ◯: when thickness of the cured portion is 1 mm or more        4) Weather Resistance Test

The accelerated weather resistance test was conducted in accordance withJIS B-7753, to determine resistance to weather:

-   Analyzer: Sunshine Carbon Arc weatherometer-   Light irradiation/rainfall cycles: Irradiation for 120    minutes/rainfall for 18 minutes-   Black panel temperature: 63±2° C.-   Tank inside temperature: 40±2° C.-   Total light irradiation time: 500 hours

The surface state of tested test piece was visually observed, toevaluate its resistance to weather according to the following threegrades:

-   ◯: No cracks or molten portion observed-   Δ: Cracks or molten portion observed slightly-   ×: Cracks or molten portion observed

The results are given in Table N1.

TABLE N1 EXAMPLE N REFERENCE EXAMPLE N 1 2 3 4 1 2 3 4 5 6Silyl-containing polymers PRODUCTION (P) 100 100 100 100 — — — — — —EXAMPLE 1 COMPARATIVE P. EXAMPLE 1 — — — — 100 — — — — — COMPARATIVE P.EXAMPLE 2 — — — — — 100 — — — — COMPARATIVE P. EXAMPLE 3 — — — — — — 100— — — COMPARATIVE P. EXAMPLE 4 — — — — — — — 100 — — COMPARATIVE P.EXAMPLE 5 — — — — — — — — 100 — COMPARATIVE P. EXAMPLE 6 — — — — — — — —— 100 Epoxy resin #828 50 50 50 50 50 50 50 50 50 50 Silane couplingagent 1 2 5 7.5 2 2 2 2 2 2 Silanol condensing catalyst 1 1 1 1 1 1 1 11 1 Epoxy curing catalyst 5 5 5 5 5 5 5 5 5 5 M₅₀ 14.9 30.1 23.7 21.632.7 36.9 27.4 24.9 37.9 10.7 M₁₀₀ 29.7 55.4 51.3 50.7 59.6 64.4 46.341.8 67.1 21.2 T_(B) (kgf/cm²) 78.1 86.3 80.1 77.7 90.5 77.7 74.4 112121 68.2 E_(B) (%) 180 131 111 107 158 125 180 314 189 250 Shearstrength (kgf/cm²) 91 138 133 131 147 180 100 143 92 100 Curing speed ◯◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ Resistance to weather ◯ ◯ ◯ ◯ X X X X X X

Examples O Series Production Example 1

[Production of Silyl-containing ethylene/propylene/5-vinyl-2-norborneneRandom Copolymer Rubber]

The three-component copolymerization was effected continuously in astainless steel polymerization reactor having an essential capacity of100 L, equipped with agitator blades (agitating rotation speed: 250rpm), wherein hexane, ethylene, propylene and 5-vinyl-2-norbornene werecontinuously supplied at 60 L, 2.5 kg, 4.0 kg and 380 g per hour,respectively, from the reactor side into the liquid phase, and hydrogen,VO(OC₂H₅)₂Cl and Al (Et)_(1.5)Cl_(1.5) as the catalysts at 700 L, 45mmols and 315 mmols per hour, respectively, also continuously.

The copolymerization effected under the above conditions produced theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber in aform of uniform solution.

A small quantity of methanol was added to the polymer solution,continuously withdrawn from the reactor bottom, to terminate thepolymerization. The polymer was separated from the solvent bysteam-stripping the solution, and dried at 55° C. for 48 hours under avacuum.

The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber thusproduced contained ethylene at 68% by mol, and had an iodine value of10, intrinsic viscosity [η] of 0.2 dl/g, and Mw/Mn of 15.

Two % toluene solution (0.3 g) of chloroplatinic acid and 1.5 g ofmethyldimethoxysilane were added to 100 g of theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber, andthey were allowed to react with each other at 120° C. for 2 hours. Theexcess methyldimethoxysilane and the solvent were distilled off from theeffluent. This produced 101.5 g of theethylene/propylene/5-vinyl-2-norbornene random copolymer rubbercontaining dimethoxymethylsilyl group.

Reference Production Examples 1 and 2

The polymers were prepared in REFERENCE PRODUCTION EXAMPLES 1 and 2 inaccordance with the respective methods of PRODUCTION EXAMPLES 1 and 3,respectively, disclosed by Japanese Patent Laid-Open Publication No.280217/1987.

Example O1, and Reference Examples O1 and O2

A mixture containing the copolymer rubber as the component (A2),prepared in PRODUCTION EXAMPLE 1, was prepared for EXAMPLE O1. It wascomposed of 100 parts of the copolymer rubber, 50 parts of a bisphenol Atype epoxy resin (Yuka Shell Epoxy, Epikote #828™), 1 part of abisphenol type antioxidant (Ouchishinko Chemical Industrial Co., NocracNS-6™), 1 part of N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane(silicon compound as the component (Q) for the present invention), 1part of diphenyl silanediol (silicon compound as the component (R) forthe present invention), 2 parts of an organotin-based compound (SankyoOrganic Chemicals, Ltd., #918™) as the silanol condensing catalyst, 5parts of 2,4,6-tris(dimethylaminomethyl)phenol as the epoxy resin curingagent, and 0.4 part of water, all by weight. These components were wellmixed with each other, and the mixture was poured into a polyethyleneframe carefully to prevent the bubbles from entering the frame, where itwas cured at 23° C. for 1 day and 50° C. for another 3 days into the 3mm thick sheet. The similar procedures were repeated for preparation ofthe mixtures and sheets containing the polymers prepared in REFERENCEPRODUCTION EXAMPLES 1 and 2 (REFERENCE EXAMPLES O1 and O2).

The composition prepared in each of EXAMPLE O1, and REFERENCE EXAMPLESO1 and O2 was tensile-tested using the dumbbell-shaped test piece, andalso measured for curing speed and resistance to weather by thefollowing methods. The results are given in Table O1.

1) Tensile Test Using the Dumbbell-Shaped Test Piece

The cured sheet was stamped out into the No. 3 dumbbell-shaped testpiece in accordance with JIS K-6301. It was stretched at 500 mm/minute,to determine its breaking strength (T_(B)) and breaking elongation(E_(B)).

Curing speed and resistance to weather were determined by the followingmethods.

1) Curing Speed

The composition comprising the major ingredient and the catalyst wasmeasured for its film expandability at room temperature, i.e., curingspeed.

The curable composition prepared in each of EXAMPLE and REFERENCEEXAMPLES was cured at 23° C. and 50% RH for 24 hours in a mold (20 by 80by 5 mm in size), and thickness of the cured portion was measured by adial gauge of weak spring force to 0.1 mm.

(Evaluation Standards)

-   -   ×: when thickness of the cured portion is less than 1 mm    -   ◯: when thickness of the cured portion is 1 mm or more        2) Weather Resistance Test

The accelerated weather resistance test was conducted in accordance withJIS B-7753, to determine resistance to weather:

-   Analyzer: Sunshine Carbon Arc weatherometer-   Light irradiation/rainfall cycles: Irradiation for 120-   minutes/rainfall for 18 minutes-   Black panel temperature: 63±2° C.-   Tank inside temperature: 40±2° C.-   Total light irradiation time: 500 hours

The surface state of tested test piece was visually observed, toevaluate its resistance to weather according to the following threegrades:

TABLE O1 Tensile properties T_(B) E_(B) Resistance to (kg/cm²) (%)Curing speed weather EXAMPLE O1 35 380 ∘ ∘ REFERENCE 48 410 ∘ x EXAMPLEO1 REFERENCE 25 210 x x EXAMPLE O2 ∘: No cracks or molten portionobserved Δ: Cracks or molten portion observed slightly x: Cracks ormolten portion observed

Examples O2 to O4, and Reference Examples O3 TO O5

The cured sheet was prepared in the same manner as in EXAMPLE O1 foreach of EXAMPLES O2 to O4, except that diphenyl silanediol as thecomponent (R) for the present invention was replaced by 0.5 part ofbis(hydroxydimethylsilyl)benzene and 0.5 part ofpolydimethyl-diphenylsiloxane with terminal diphenyl silanol group(Petrarch Systems Inc., PS-084™) or 0.5 part of silicone varnish havingsilanol group (Shin-Etsu Chemical Co., Ltd., KR-212™), all by weight, tomeasure T_(B) and E_(B). The cured sheet was prepared similarly usingthe composition prepared in REFERENCE EXAMPLE O1 for each of REFERENCEEXAMPLES O3 to O5. The results are given in Table O2.

TABLE O2 Tensile properties T_(B) E_(B) Resistance Types of component(R) (kg/cm²) (%) Curing speed to weather EXAMPLE O2Bis(hydroxydimethylsilyl) 67 550 ◯ ◯ benzene EXAMPLE O3 PS-084 65 800 ◯◯ EXAMPLE O4 KR-212 73 720 ◯ ◯ REFERENCE Bis(hydroxydimethylsilyl) 55510 ◯ X EXAMPLE O3 benzene REFERENCE PS-084 55 750 ◯ X EXAMPLE O4REFERENCE KR-212 63 660 ◯ X EXAMPLE O5

Examples O5 TO O8, and Reference Examples O7 to O12

The adhesion test piece was prepared from the composition prepared ineach of EXAMPLES O1 to O4 by the following procedure, to measure itsadhesion strength in EXAMPLES O5 to O8. The results are shown in TableO3.

Methods of Preparing the Test Piece and Testing for the Tensile ShearStrength (in Accordance with JIS K-6850)

An aluminum plate (A-1050P aluminum plate, 100 by 25 by 2 mm in size,specified by JIS H-4000) was wiped lightly with acetone, on which theresin composition was spread by a spatula to an area of around 25 by12.5 mm and thickness of 0.05 mm. The coated surfaces of the two plateswere attached face-to-face and manually pressed against each other. Thecoated test pieces were fixed, and the resin composition was cured at23° C. for 1 day and 50° C. for another 3 days. Then, they werestretched at 5 mm/minute away from each other until their cured resinwas fractured. The maximum load value measured at which the cured resinwas fractured was divided by the sheared area to find the tensile shearstrength.

Methods of Preparing the Test Piece and Testing for the T Type ReleasingStrength

An aluminum plate (A-1050P aluminum plate, 200 by 25 by 0.1 mm in size,specified by JIS H-4000) was wiped lightly with acetone, on which theresin composition was spread by a spatula to an area of around 100 by 25mm and thickness of 0.3 mm. The coated surfaces of the two plates wereattached face-to-face and pressed against each other by a 5 kg handroller repeatedly 5 times in such a way to avoid back-and-forth motion.The resin composition was cured at 23° C. for 1 day and 50° C. foranother 3 days. Then, the test piece thus prepared was set in a tensiletester in a T-shape, and stretched at 200 mm/minute until the adhesiveportion was fractured. The strength at which the adhesive portion wasfractured was measured as the T-type releasing strength.

TABLE O3 Adhesion strength Tensile shear T type releasing Types ofStrength strength compositions used (kg/cm²) (kg/25 mm) EXAMPLES O5EXAMPLE O1 142 13.2 O6 EXAMPLE O2 116 10.7 O7 EXAMPLE O3 104 11.1 O8EXAMPLE O4 105 8.9

Example O9

The curable resin composition was prepared in EXAMPLE O1 using thepolymer prepared in PRODUCTION EXAMPLE 1. It comprised 100 parts of thepolymer, 50 parts of Epikote #828™, 1 part of Nocrac NS-6™, 1 part ofN-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, 1 part of diphenylsilanediol, 2 parts of #918™, and 5 parts of2,4,6-tris(dimethylaminomethyl)phenol. These components were well mixedwith each other in a nitrogen atmosphere in such a way to preventcontamination with moisture in air.

The test piece was prepared from the above composition following theabove-described method of preparing the test piece, and cured at 23° C.for 1 day and 50° C. for another 3 days, to measure its adhesionstrength. It had a tensile shear strength of 126 kg/cm² and a T-typereleasing strength of 9.0 kg/25 mm (EXAMPLE O9).

Examples P Series Production Example 1

[Production of Silyl-containing ethylene/propylene/5-vinyl-2-norborneneRandom Copolymer Rubber]

The three-component copolymerization was effected continuously in astainless steel polymerization reactor having an essential capacity of100 L, equipped with agitator blades (agitating rotation speed: 250rpm), wherein hexane, ethylene, propylene and 5-vinyl-2-norbornene werecontinuously supplied at 60 L, 2.5 kg, 4.0 kg and 380 g per hour,respectively, from the reactor side into the liquid phase, and hydrogen,VO(OC₂H₅)₂Cl and Al (Et)_(1.5)Cl_(1.5) as the catalysts at 700 L, 45mmols and 315 mmols per hour, respectively, also continuously.

The copolymerization effected under the above conditions produced theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber in aform of uniform solution.

A small quantity of methanol was added to the polymer solution,continuously withdrawn from the reactor bottom, to terminate thepolymerization. The polymer was separated from the solvent bysteam-stripping the solution, and dried at 55° C. for 48 hours under avacuum.

The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber thusproduced contained ethylene at 68% by mol, and had an iodine value of10, an intrinsic viscosity [η] of 0.2 dl/g, and Mw/Mn of 15.

Two % toluene solution (0.3 g) of chloroplatinic acid and 1.5 g ofmethyldimethoxysilane were added to 100 g of theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber, andthey were allowed to react with each other at 120° C. for 2 hours. Theexcess methyldimethoxysilane and the solvent were distilled off from theeffluent. This produced 101.5 g of theethylene/propylene/5-vinyl-2-norbornene random copolymer rubbercontaining dimethoxymethylsilyl group.

Examples P1 and P2, and Comparative Examples P1 to P3

A mixture containing the copolymer rubber containing dimethoxysilylgroup, prepared in PRODUCTION EXAMPLE P1, was prepared for each ofEXAMPLES P1 and P2, and COMPARATIVE EXAMPLES P1 to P3. It was composedof the copolymer rubber, a paraffin-based process oil (Idemitsu Kosan,Diana Process Oil PS-32™), colloidal calcium carbonate (Shiraishi K. K.,EDS-D10A™), limestone powder (Maruo Calcium, Snowlite SS™), talc (FujiTalc Kogyo, Talc LMR™), Na₂SO₄.10H₂O, (Wako Jun-yaku Kogyo), andγ-isocyanate propyltriethoxysilane as a silane coupling agent (NipponUnicar, Y-₉₀₃₀™). Table P1 gives each composition in parts by weight.The mixture was well kneaded by a 3-paint roll unit, to produce themajor ingredient for each of the examples.

Each of the major ingredients was evaluated for its thready property bya spatula.

The major ingredient was incorporated with dibutyl tinbisacetylacetonate (NITTO KASEI Co., Neostann U-₂₂₀™) to prepare themixture of 404/2 ratio by weight. The components were well kneadedmanually, and the resultant mixture was formed into a sheet in a 2 mmthick aluminum frame lined with a Teflon sheet while breaking thebubbles in the composition by a spatula. It was cured in an oven at 23°C. for 7 days and 50° C. for 7 days. The cured sheet was stamped outinto the No. 3 dumbbell-shaped test piece in accordance with JISK-6251/1993, the “method of tensile testing vulcanized rubber,” wherethe test piece was stretched at 500 mm/minute by an autograph (Shimadzu,Autograph AG-2000A) in a constant-temperature chamber kept at 23° C. and50±10% RH.

The cured test piece for hardness measurement was prepared in thefollowing procedure. The major ingredient was incorporated with a curingcatalyst (NITTO KASEI, Neostann U-220™) to prepare the mixture of 404/2ratio by weight. The components were well kneaded, and the resultantmixture was cured into a rectangular parallelepiped test piece in aframe (12 by 12 by 50 mm in size) lined with a Teflon sheet under thestandard conditions of 23° C. for 7 days and 50° C. also for 7 days, tomeasure its hardness. Hardness of the rod-shaped test piece was measuredin accordance with JIS K-6301/1975 by the spring type hardness test Amethod using a rubber type hardness meter (Shimadzu, Hardness meter200). A total of 5 measurements were made for each composition, and theaverage value was reported.

Table P1 gives the composition, viscosity (at 10 rpm) of the majoringredient, and thready property, dumbbell tensile test results,hardness, curing speed and resistance to weather of each composition.

Thready property was evaluated according to the following two-gradesystem:

-   ◯: The composition is low in thready property, and easy to finish by    spatula-   ×: The composition is high in thready property, and difficult to    finish by spatula

M50, T_(max) and E_(max) in Table P1 are 50% tensile stress, maximumtensile stress and elongation at the maximum load, respectively.

Curing speed and resistance to weather were measured by the followingmethods:

1) Curing Speed

The composition comprising the major ingredient and the catalyst wasmeasured for its film expandability at room temperature, i.e., curingspeed.

The curable composition was cured at 23° C. and 50% RH for 24 hours in amold (20 by 80 by 5 mm in size), and thickness of the cured portion wasmeasured by a dial gauge of weak spring force to 0.1 mm.

(Evaluation Standards)

-   -   ×: when thickness of the cured portion is less than 1 mm    -   ◯: when thickness of the cured portion is 1 mm or more        2) Weather Resistance Test

The accelerated weather resistance test was conducted in accordance withJIS B-7753, to determine resistance to weather:

-   Analyzer: Sunshine Carbon Arc weatherometer-   Light irradiation/rainfall cycles: Irradiation for 120-   minutes/rainfall for 18 minutes-   Black panel temperature: 63±2° C.-   Tank inside temperature: 40±2° C.-   Total light irradiation time: 500 hours

The surface state of tested test piece was visually observed, toevaluate its resistance to weather according to the following threegrades:

-   ◯: No cracks or molten portion observed-   Δ: Cracks or molten portion observed slightly-   ×: Cracks or molten portion observed

The results are given in Table P1.

Comparative Examples P4 to P8

An isobutylene polymer having a reactive silicon group was synthesizedin accordance with the method described in Japanese Patent Laid-OpenPublication No. 316804/1998, paragraphs 0049 to 0055.

The composition was prepared for each of COMPARATIVE EXAMPLES P4 to P8in the same manner as in each of EXAMPLES P1 and P2, and COMPARATIVEEXAMPLES P1 to P3, respectively, except that the copolymer rubbercontaining dimethoxysilyl group was replaced by the isobutylene polymerhaving a reactive silicon group. Several properties of the compositionswere measured. The results are shown in Table P2

TABLE P1 EXAMPLE P COMPARATIVE EXAMPLE P Compositions Additives 1 2 1 23 Major ingredients Polymer produced in 100 100 100 100 100 (parts byweight) PRODUCTION EXAMPLE PS-32 100 100 100 100 100 EDS-D10A 100 50 200— — Snowlite SS 50 200 — 300 — LMR 100 100 — — 200 Na₂SO₄.10H₂O 2 2 2 22 Y-9030 2 2 2 2 2 Curing catalyst U-220 2 2 2 2 2 (parts by weight)Thready property ◯ ◯ ◯ X X Tensile characteristics M50 (kgf/cm²) 7.907.91 3.52 4.12 9.69 Tmax (kgf/cm²) 11.7 12.6 11.6 8.8 13.1 Emax (%) 8583 215 118 62 JIS Hardness A 34 34 24 28 38 Curing speed ◯ ◯ ◯ ◯ ◯Resistance to weather ◯ ◯ ◯ ◯ ◯

TABLE P2 COMPARATIVE EXAMPLE P Compositions Additives 4 5 6 7 8 Majoringredients Note (1) 100 100 100 100 100 (parts by weight) PS-32 100 100100 100 100 EDS-D10A 200 — — 100 50 Snowlite SS — 300 — 50 200 LMR — —200 100 100 Na₂SO₄.10H₂O 2 2 2 2 2 Y-9030 2 2 2 2 2 Curing catalystU-220 2 2 2 2 2 (parts by weight) Thready property ◯ X X ◯ ◯ Tensile M50(kgf/cm²) 4.1 4.8 11.3 9.0 9.2 characteristics Tmax (kgf/cm²) 13.8 10.415.4 13.8 14.7 Emax (%) 248 132 70 93 95 JIS Hardness A 29 33 39 38 38Curing speed X X X X X Resistance to Δ Δ Δ Δ Δ weather Note (1): Thepolymer used in EXAMPLE described in Japanese Patent Laid-OpenPublication No.316804/1998

It is apparent that the following findings are derived from the resultsgiven in Tables P1 and P2.

The composition prepared in each of EXAMPLES P1 and P2 using thesilyl-containing copolymer rubber is excellent in workability. The curedproduct is excellent in mechanical strength and hardness, and theseproperties are well-balanced. Moreover, it has sufficient resistance toweather and curing speed.

The composition prepared in each of COMPARATIVE EXAMPLES P1 to P3, whichwas free of calcium carbonate or talc although containing thesilyl-containing copolymer rubber, was less balanced between theseproperties mentioned above.

The composition prepared in each of COMPARATIVE EXAMPLES P4 to P8, whichwas free of the silyl-containing copolymer rubber, was less balancedbetween these properties, and less resistant to weather or lower incuring speed.

Examples Q Series

The composition, the iodine value, the intrinsic viscosity [η] and themolecular weight distribution (Mw/Mn) of the copolymer rubber used ineach of EXAMPLES and COMPARATIVE EXAMPLES were determined by the methodsdescribed earlier.

Production Example

[Production of Silyl-containing ethylene/propylene/5-vinyl-2-norborneneRandom Copolymer Rubber (A-1)]

The three-component copolymerization was effected continuously in astainless steel polymerization reactor having an essential capacity of100 L, equipped with agitator blades (agitating rotation speed: 250rpm), wherein hexane, ethylene, propylene and 5-vinyl-2-norbornene werecontinuously supplied at 60 L, 2.5 kg, 4.0 kg and 380 g per hour,respectively, from the reactor side into the liquid phase, and hydrogen,VO(OEt)₂Cl and Al(Et)_(1.5)Cl_(1.5) as the catalysts at 700 L, 45 mmolsand 315 mmols per hour, respectively, also continuously.

The copolymerization effected under the above conditions produced theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A₀-1)in a form of uniform solution.

A small quantity of methanol was added to the polymer solution,continuously withdrawn from the reactor bottom, to terminate thepolymerization. The polymer was separated from the solvent bysteam-stripping the solution, and dried at 55° C. for 48 hours under avacuum.

The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber(A₀-1) thus produced contained ethylene at 68% by mol, and had anintrinsic viscosity [η] of 0.2 dl/g determined in decalin kept at 135°C., iodine value (IV) of 10 (g/100 g) and Mw/Mn of 15.

Two % toluene solution (0.3 part by weight) of chloroplatinic acid and1.5 parts by weight of methyldimethoxysilane were added to 100 parts byweight of the ethylene/propylene/5-vinyl-2-norbornene random copolymerrubber (A₀-1), and they were allowed to react with each other at 120° C.for 2 hours. The excess methyldimethoxysilane and the solvent (toluene)were distilled off from the effluent. This produced 101.5 parts byweight of the ethylene/propylene/ 5-vinyl-2-norbornene random copolymerrubber (A-1) containing dimethoxymethylsilyl group (—Si(CH₃)(OCH₃)₂).

Example Q1

A mixture containing the silyl-containingethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1)prepared in PRODUCTION EXAMPLE, was prepared for EXAMPLE Q1. It wascomposed of 100 parts of the copolymer rubber (A-1), 90 parts of aparaffin-based process oil (Idemitsu Kosan, Diana Process Oil PS-32™) asthe plasticizer, 360 parts of limestone powder (Shiraishi Calcium,Whiton SB™) as the filler, 5 parts of salt cake Na₂SO₄.10H₂O as thewater source, 1 part oftetrakis-[methylene-3-(3′,5′-di-t-butyl-4-hydroxyphenyl) propionate]methane (Ciba-Geigy Japan, Irganox 1010™) as the aginginhibitor, 1 part of 2-(2′-hydroxy-3′,5′-t-butyl)-5-chlorobenzotriazole(Ciba-Geigy Japan, Tinuvin 327™) as the stabilizer, 1 part ofbis-(2,2,6,6-tetramethyl-4-piperidyl)cebacate (Sankyo, Sanol LS-770™), 5parts of a thixotropy imparting agent (Kusumoto Kasei, Disparlon #305™),2 parts of γ-isocyanate propyltriethoxysilane (Nippon Unicar, Y-9030™)as the silane coupling agent, and 3 parts of nickeldimethyldithiocarbamate (Sanshin Kagaku Kogyo, Sandant NBC™),represented by the following structural formula, as the lightstabilizer, all parts by weight. It was sufficiently kneaded to mix thecomponents by a 3-paint roll unit, to prepare the major ingredient.

The curing agent was prepared by the following procedure: a mixturecomprising 10 parts of a paraffin-based process oil (Idemitsu Kosan,Diana Process Oil PS-32™), 25 parts of limestone powder (ShiraishiCalcium, Whiton SB™), 4 parts of tetravalent tin compound (NITTO KASEI,U-220™) as the curing catalyst, and 2.5 parts of carbon black(Mitsubishi Chemical, CB#30™), all parts by weight, was manually kneadedin a disposal cup and stirred repeatedly 3 times at 10,000 rpm each for10 minutes by a homogenizer (Nihon Seiki Sesakusho, Excel AutoHomogenizer)

The test piece was prepared in accordance with JIS A-5758-1992specifying the method of preparing the test piece for tensile adhesiontest; the composition comprising 14 parts by weight of theabove-described major ingredient and 1 part by weight of the curingagent was put in the H-shape frame of glass or aluminum substrate, afterbeing sufficiently kneaded. The composition was cured in an oven underthe conditions of 23° C. for 7 days and 50° C. for 7 days. The heat rayreflective glass sheets (Central Glass, SGY-32™ and TCB-35™, 5 by 5 by0.6 cm in size) surface-coated with TiO₂ by sputtering were used as thesubstrates for the H-shaped frames. Each H-shape frame was washed withmethylethyl ketone (Wako-Junyaku, special grade) and wiped with cleancotton cloth, before it was filled with the composition.

The light-resistant adhesion test was conducted using the H-shaped testpiece prepared as described above, wherein its H-type mechanicalproperties before and after the test were measured. The results aregiven in Table Q1. In the test, the H-type tensile test piece, put in aSunshine superlong-life weathermeter (Suga Shikenki, WEL-SUN-HC) withblack panel temperature kept at 63° C., was irradiated with lightemitted from sunshine carbon as the light source, and taken out from theanalyzer after 480 hours.

The H-shape test piece thus prepared was tested by the method of testingtensile adhesion in accordance with JIS A-5758/1992 at a tensile speedof 50 mm/minute in a constant-temperature chamber kept at 23° C. and65±5% RH. The cohesion fracture (CF)/thin-coat fracture (TCF)/adhesionfracture (AF) ratio shown in the tables was determined by visualobservation of the cross-sections of the tensile-tested pieces.

The cohesion fracture means the fracture of the cured compositionitself, not at the interface between the base and cured composition,indicating that the cured composition is adhered to the base at a highadhesion strength. The adhesion fracture means the separation of thebase and cured composition from each other at the interface, indicatingthat the cured composition is adhered to the base at a low adhesionstrength. The thin-coat fracture is the cohesion fracture at theinterface, indicating that its adhesion strength is medium between thosefor the above two fracture modes.

The weather resistance test was conducted by the following procedure.The results are also given in Table Q1.

Weather Resistance Test

The accelerated weather resistance test was conducted in accordance withJIS B-7753 under the following conditions::

-   Analyzer: Sunshine Carbon Arc weatherometer-   Light irradiation/rainfall cycles: Irradiation for 120-   minutes/rainfall for 18 minutes-   Black panel temperature: 63±2° C.-   Tank inside temperature: 40±2° C.-   Total light irradiation time: 500 hours

Comparative Examples Q1 to Q3

The same procedures as used for EXAMPLE Q1 were repeated, except that 3parts by weight of nickel dimethyldithiocarbamate (Sanshin Kagaku Kogyo,Sandant NBC™) as the light stabilizer was not incorporated (COMPARATIVEEXAMPLE Q1), 3 parts by weight of2-(2′-hydroxy-3′,5′-t-butyl)-5-chlorobenzotriazole (Ciba-Geigy Japan,Tinuvin 327™) was incorporated as the non-nickel-based stabilizer(COMPARATIVE EXAMPLE Q2), and 5 parts by weight ofbis(2,2,6,6-tetramethyl-4-piperidyl)cebacate (Sankyo, Sanol LS-770™) wasincorporated as the non-nickel-based stabilizer (COMPARATIVE EXAMPLEQ3). The results are given in Table Q1.

TABLE Q1 M₅₀ T_(max) E_(max) Fractured conditions (%) (kgf/cm²)(kgf/cm²) (%) CF TFC AF Resistance to weather Before Testing EXAMPLE Q14.4 5.8 60 100 0 0 No cracks or molten portion observed COMPARATIVE 4.35.9 62 99 1 0 No cracks or molten EXAMPLE Q1 portion observedCOMPARATIVE 4.3 5.8 63 100 0 0 No cracks or molten EXAMPLE Q2 portionobserved COMPARATIVE 4.3 5.6 60 100 0 0 No cracks or molten EXAMPLE Q3portion observed After Testing EXAMPLE Q1 3.2 4.7 75 100 0 0 COMPARATIVE3.0 3.2 52 0 2 98 EXAMPLE Q1 COMPARATIVE 2.9 3.4 54 0 1 99 EXAMPLE Q2COMPARATIVE 3.1 3.1 50 1 0 99 EXAMPLE Q3

As shown in Table Q1, the composition prepared in each of EXAMPLE Q1 andCOMPARATIVE EXAMPLES Q1 to Q3 exhibited good adhesion to thesurface-treated SGY-32 glass substrate before the weather-resistantadhesion test. After the test, on the other hand, only the test pieceprepared in EXAMPLE Q1 showed the cohesion fracture, and the others theadhesion fracture. These results indicate that incorporation of theNi-based stabilizer (Sandant NBC™) improves light-resistant adhesion.

Example Q2 and Comparative Example Q4

The same procedures as used for EXAMPLE Q1 were repeated for EXAMPLE Q2,except that 3 parts by weight of nickel dimethyldithiocarbamate (SanshinKagaku Kogyo, Sandant NBC™) was replaced by 3 parts by weight of nickel[2,2′-thiobis(4-t-octylphenolate)]-n-butylamine (ACC, SYASORB UV1084),represented by the following formula, also as the Ni-based lightstabilizer:

The same procedures as used for EXAMPLE Q2 were repeated for COMPARATIVEEXAMPLE Q4, except that 3 parts by weight of nickel [2,2′-thiobis(4-t-octylphenolate)]-n-butylamine (ACC, SYASORB UV1084™) was replacedby 3 parts by weight of 3,5-di-t-butyl-4-hydroxybenzoic acid-n-hexadecylester (ACC, SYASORB UV2908™), represented by the following formula, asthe non-Ni-based light stabilizer:

The results are given in Table Q2.

Example Q3 and Comparative Example Q5

The same procedures as used for EXAMPLE Q1 were repeated for EXAMPLE Q3,except that quantity of limestone powder (Shiraishi Calcium, Whiton SB™)was reduced from 25 to 20 parts by weight. The same procedures as usedfor EXAMPLE Q3 were repeated for COMPARATIVE EXAMPLE Q5, except that 3parts by weight of nickel dimethyldithiocarbamate (Sanshin Kagaku Kogyo,Sandant NBC™) as the Ni-based light stabilizer was replaced by 3 partsby weight of 2,4-dibutylphenyl-3′,5′-di-t-butyl-4′-hydroxybenzoate (ACC,SYASORB 712™), represented by the following formula, as the non-Ni-basedlight stabilizer:

The results are given in Table Q2.

TABLE Q2 M₅₀ T_(max) E_(max) Fractured conditions (%) (kgf/cm²)(kgf/cm²) (%) CF TFC AF Resistance to weather EXAMPLE Q2 3.2 4.4 78 1000 0 No cracks or molten portion observed EXAMPLE Q3 3.3 4.8 80 100 0 0No cracks or molten portion observed COMPARATIVE 3.0 3.2 52 0 1 99 Nocracks or molten EXAMPLE Q4 portion observed COMPARATIVE 3.2 3.2 50 0 298 No cracks or molten EXAMPLE Q5 portion observed

Examples R Series

The composition, the iodine value, the intrinsic viscosity [η] and themolecular weight distribution (Mw/Mn) of the copolymer rubber used ineach of EXAMPLES and COMPARATIVE EXAMPLES were determined by the methodsdescribed earlier.

Curing speed and resistance to weather tests were conducted in EXAMPLESand COMPARATIVE EXAMPLES by the following methods:

(1) Curing Speed Test

The compositions prepared in EXAMPLES and COMPARATIVE EXAMPLES, werecured at 23° C. and 50% RH for 24 hours in a mold (20 by 80 by 5 mm insize), and then released from the mold. Thickness of the cured portionwas measured by a dial gauge of weak spring force to 0.1 mm, to evaluateits curing speed. It was marked with ◯ when its thickness was more than1 mm, Δ when it was 0.5 to 1 mm, and × when it was less than 0.5 mm

(2) Weather Resistance Test

The weather resistance test was conducted in accordance with JIS B-7753using a Sunshine Carbon Arc weatherometer, to determine resistance toweather:

<Testing Conditions>

-   Light irradiation/rainfall cycles: Irradiation for 120-   minutes/rainfall for 18 minutes-   Black panel temperature: 63±2° C.-   Tank inside temperature: 40±2° C.-   Total light irradiation time: 500 hours    <Evaluation Standards for Resistance to Weather>-   ◯: No cracks or molten portion observed on one side of the tested    piece-   Δ: Cracks or molten portion observed slightly on one side of the    tested piece-   ×: Cracks or molten portion observed on one side of the tested piece

Production Example R1

[Production of Silyl-containing ethylene/propylene/5-vinyl-2-norborneneRandom Copolymer Rubber (A-1)]

The three-component copolymerization was effected continuously in astainless steel polymerization reactor having an essential capacity of100 L, equipped with agitator blades (agitating rotation speed: 250rpm), wherein hexane, ethylene, propylene and 5-vinyl-2-norbornene werecontinuously supplied at 60 L, 2.5 kg, 4.0 kg and 380 g per hour,respectively, from the reactor side into the liquid phase, and hydrogen,VO(OEt)₂Cl and Al(Et)_(1.5)Cl_(1.5) as the catalysts at 700 L, 45 mmolsand 315 mmols per hour, respectively, also continuously.

The copolymerization effected under the above conditions produced theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A₀-1)in a form of uniform solution.

A small quantity of methanol was added to the polymer solution,continuously withdrawn from the reactor bottom, to terminate thepolymerization. The polymer was separated from the solvent bysteam-stripping the solution, and dried at 55° C. for 48 hours under avacuum.

The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber(A₀-1) thus produced contained ethylene at 68% by mol, and had anintrinsic viscosity [η] of 0.2 dl/g determined in decalin kept at 135°C., iodine value (IV) of 10 (g/100 g) and Mw/Mn of 15.

Two % toluene solution (0.3 g) of chloroplatinic acid and 1.5 g ofmethyldimethoxysilane were added to 100 g of theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A₀-1),and they were allowed to react with each other at 120° C. for 2 hours.The excess methyldimethoxysilane and the solvent (toluene) weredistilled off from the effluent. This produced 101.5 g of the

-   -   ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber        (A-1) containing dimethoxymethylsilyl group (—SiCH₃(OCH₃)₂).

Production Example R2

Two hundred grams of a polypropylene oxide with allyl ether group at 97%of the total terminals and having an average molecular weight of 5,000,was charged in a 500 mL four-mouthed flask, to which 100 μL of a 10%ethanol solution of chloroplatinic acid was added and thenmethyldimethoxysilane was added dropwise at 50° C., and they wereallowed to react with each other at 80° C. for around 3 hours.

The resultant reaction product was a polypropylene oxide having 1.7structures represented by the following formula in one molecule and anaverage molecular weight of around 5,200, as revealed by the ¹H-NMRanalysis:(CH₃O)₂Si(CH₃)(CH₂)₂CH₂O—

Examples R1 to R6

The silyl-containing ethylene/propylene/5-vinyl-2-norbornene randomcopolymer rubber (A-1), prepared by PRODUCTION EXAMPLE R1, was used toprepare the toluene solution of uniform composition, described in TableR1, for each of EXAMPLES R1 to R6.

Each solution was cured at room temperature for 1 day and at 50° C. foranother 4 days in an about 3 mm thick frame, and then treated at 50° C.for 2 hours under a vacuum of 2 to 3 mmHg, to completely evaporatetoluene.

The resultant cured sheet was put in a hot wind type drier kept at 150°C. for 20 days, to observe temporal property changes (measurement ofresistance to heat). The results are given in Table R1, wherein theresistance to heat was evaluated by the three grades, ◯: no cracks ormolten portion observed, Δ: cracks or molten portion observed slightly,and ×: cracks or molten portion observed; and NISSAN DLTP: sulfidecarboxylate ester-based antioxidant (NOF Corp.), Nocrac 300:sulfur-containing hindered phenol (Ouchishinko Chemical Industries Co.,)and Irgano 1010: hindered phenol (Ciba Geigy, Japan).

TABLE R1 Compositions [parts by weight] Properties Component Tin LaurylResistance Resistance Curing EXAMPLES (A1) Component (U) octylate amineToluene Water to heat to weather speed R1 100 NISSAN 1 3 0.75 50 0.5 ◯ ◯◯ DLTP R2 100 NISSAN 3 3 0.75 50 0.5 ◯ ◯ ◯ DLTP R3 100 NISSAN 5 3 0.7550 0.5 ◯ ◯ ◯ DLTP R4 100 Nocrac 300 1 3 0.75 50 0.5 ◯ ◯ ◯ R5 100 Nocrac300 3 3 0.75 50 0.5 ◯ ◯ ◯ R6 100 Nocrac 300 5 3 0.75 50 0.5 ◯ ◯ ◯Component (A1): ethylene/propylene/5-vinyl-2-norbornene random copolymerrubber (A-1)

Examples R7 to R9, and Comparative Example R1

The 1 mm thick sheet was prepared for each of EXAMPLES R7 to R9, andCOMPARATIVE EXAMPLE R1 in the same manner as in EXAMPLE R1, except thatthe sulfur-based aging inhibitor was replaced by the additive given inTable R2 to prepare the composition. A test tube type rubber agingtester was used to measure the time required for the sheet to becompletely decomposed at 150° C. and start to flow.

The results are given in Table R2.

Comparative Example R2

The sheet was prepared for COMPARATIVE EXAMPLE R2 in the same manner asin EXAMPLE R7, except that the silyl-containingethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1)prepared in PRODUCTION EXAMPLE R1 was replaced by the polymer preparedin PRODUCTION EXAMPLE R2, and tested also in the same manner. Theresults are given in Table R2.

TABLE R2 COMPARATIVE EXAMPLE R EXAMPLE R 7 8 9 1 2 NISSAN DLTP 1 — 1 — 1[parts by weight] Nocrac 300 [parts by weight] — 1 1 — — Resistance toheat ◯ ◯ ◯ Δ Δ Resistance to weather ◯ ◯ ◯ Δ X Curing speed ◯ ◯ ◯ ◯ ◯

The cured composition prepared in each of EXAMPLES R1 to R9 andCOMPARATIVE EXAMPLES R1 and R2 was tested for resistance to weatherfollowing the method described earlier. As a result, no cracks wereobserved in the test pieces prepared in EXAMPLES R1 to R9, but observedin those prepared in COMPARATIVE EXAMPLES R1 and R2.

Examples S Series

The composition, the iodine value, the intrinsic viscosity [η] and themolecular weight distribution (Mw/Mn) of the copolymer rubber used ineach of EXAMPLES and COMPARATIVE EXAMPLES were determined by the methodsdescribed earlier.

Production Example

[Production of Silyl-containing ethylene/propylene/5-vinyl-2-norborneneRandom Copolymer Rubber (A-1)]

The three-component copolymerization was effected continuously in astainless steel polymerization reactor having an essential capacity of100 L, equipped with agitator blades (agitating rotation speed: 250rpm), wherein hexane, ethylene, propylene and 5-vinyl-2-norbornene werecontinuously supplied at 60 L, 2.5 kg, 4.0 kg and 380 g per hour,respectively, from the reactor side into the liquid phase, and hydrogen,VO(OEt)₂Cl and Al(Et)_(1.5)Cl_(1.5) as the catalysts at 700 L, 45 mmolsand 315 mmols per hour, respectively, also continuously.

The copolymerization effected under the above conditions produced theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A₀-1)in a form of uniform solution.

A small quantity of methanol was added to the polymer solution,continuously withdrawn from the reactor bottom, to terminate thepolymerization. The polymer was separated from the solvent bysteam-stripping the solution, and dried at 55° C. for 48 hours under avacuum.

The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber(A₀-1) thus produced contained ethylene at 68% by mol, and had anintrinsic viscosity [η] of 0.2 dl/g determined in decalin kept at 135°C., iodine value (IV) of 10 g/100 g and Mw/Mn of 15.

Two % toluene solution (0.3 part by weight) of chloroplatinic acid and1.5 parts by weight of methyldimethoxysilane were added to 100 parts byweight of the ethylene/propylene/5-vinyl-2-norbornene random copolymerrubber (A₀-1), and they were allowed to react with each other at 120° C.for 2 hours. The excess methyldimethoxysilane and the solvent (toluene)were distilled off from the effluent. This produced 101.5 parts byweight of the ethylene/propylene/5-vinyl-2-norbornene random copolymerrubber (A-1) containing dimethoxymethylsilyl group (—Si(CH₃)(OCH₃)₂).

Examples S1 to S5

A mixture containing the polymer prepared in PRODUCTION EXAMPLE wasprepared for each of EXAMPLES S1 to S5. It was composed of 100 parts ofthe polymer, 90 parts of a paraffin-based process oil (Idemitsu Kosan,Diana Process Oil PS-32™), 30 parts of limestone powder (Maruo Calcium,Snowlite SS™), 100 parts of colloidal calcium carbonate (Shiraishi K.K., EDS-D10A™), 100 parts of talc (Fuji Talc Kogyo, Talc LMR™), 6 partsof Na₂SO₄.10H₂O, 6 parts of china wood oil as the compound and component(V) for the present invention having an unsaturated group polymerizableon reacting with oxygen in air, 3 parts of dipentaerythritol penta- andhexa-acrylate as the photopolymerizable compounds (TOAGOSEI, AronixM-400™), and a tackifier given in Table S1 in a quantity also given inTable S1, all parts by weight. Each mixture was well kneaded by a3-paint roll unit, to produce the major ingredient for each example.

The tackifiers used in EXAMPLES S1 to S3 wereγ-glycidoxypropyltrimethoxysilane (Nippon Unicar, Silane coupling agentA-187™) as the silane coupling agent for the present invention and/orγ-isocyanatepropyltriethoxysilane (Nippon Unicar, Silane coupling agentY-9030™) in quantities given in Table S1. EXAMPLE S4 used no tackifier,while EXAMPLE S5 used 4 parts by weight of an epoxy resin as thetackifier containing no hydrolyzable silicon group (except the silanecoupling agent) (Yuka Shell Epoxy, Epikote #828™).

The curing agent was prepared by the following procedure: a mixturecomprising 10 parts of a paraffin-based process oil (Idemitsu Kosan,Diana Process Oil PS-32™), 20 parts of limestone powder (Maruo Calcium,Snowlite SS™), 4 parts of a curing catalyst (NITTO KASEI, U-22 ™), and2.5 parts of carbon black (Mitsubishi Chemical, CB#30™), all parts byweight, was manually kneaded in a disposal cup and stirred 3 times at10,000 rpm each for 10 minutes by a homogenizer (Nihon Seiki SeisakushoCo., Ltd., Excel Auto Homogenizer).

The cured test piece for tensile adhesion measurement was prepared inthe following procedure in accordance with JIS A-5758/1992. The majoringredient was incorporated with the curing agent to prepare the mixtureof 12/1 by weight. The components were well kneaded, and the resultantmixture was put in the H-shape of glass base while breaking the bubblesin the composition by a spatula, and cured in an oven, under theconditions of 23° C.×1 day+50° C.×5 days for each composition. Thesubstrate for the H-type tensile test was of float glass (Koen-sha,designated by Japan Sealant Industry Association, 3 by 5 by 0.5 cm insize) in accordance with JIS A-5758/1992, or heat ray reflective glass(Central Glass, KLS™, 5 by 5 by 0.6 cm in size) coated with thermallyfused TiOx. Each of these H-shaped bases was washed with methylethylketone (Wako-Junyaku, special grade) and wiped with clean cotton cloth,before it was filled with the composition. It was not coated with aprimer.

The H-shape test piece thus prepared for the tensile test was testedafter it was cured in the absence of primer by the method of testingtensile adhesion in accordance with JIS A-5758/1992. The test wasconducted at a tensile speed of 50 mm/minute by an autograph (Shimadzu,Autograph AG-2000A) in a constant-temperature chamber kept at 23° C. and50±10% RH, to evaluate adhesion in the absence of a primer by comparingthe tensile characteristics with fractured morphology. The results aregiven in Table S1, where the cohesion fracture (CF)/thin-coat fracture(TCF)/adhesion fracture (AF) ratio was determined by visual observationof the cross-sections of each tensile-tested piece.

Curing speed and resistance to weather were measured by the followingmethods. The results are given in Table S7.

(1) Curing Speed Test

The curable composition was cured at 23° C. and 50% RH for 24 hours in amold (20 by 80 by 5 mm in size), and then released from the mold.Thickness of the cured portion was measured by a dial gauge of weakspring force to 0.1 mm, to evaluate its curing speed. It was marked with◯ when its thickness was 1 mm or more, and × when it was less than 1 mm.

(2) Weather Resistance Test

The accelerated weather resistance test was conducted in accordance withJIS B-7753 under the following conditions, to determine resistance toweather:

-   Analyzer: Sunshine Carbon Arc weatherometer-   Light irradiation/rainfall cycles: Irradiation for 120-   minutes/rainfall for 18 minutes-   Black panel temperature: 63±2° C.-   Tank inside temperature: 40±2° C.-   Total light irradiation time: 1000 hours

TABLE S1 Tackifier Elongation at Fractured Molphologies (%)*² EXAMPLES(addition rate) Base materials max. load*¹ CF TCF AF S1 A-187 (4 parts)Float glass ◯ 100 0 0 Heat ray reflective glass: KLS ◯ 100 0 0 S2 Y-9030(4 parts) Float glass ◯ 100 0 0 Heat ray reflective glass: KLS ◯ 100 000 S3 A-187 (2 parts) Float glass ◯ 100 0 0 Y-9030 (4 parts) Heat rayreflective glass: KLS ◯ 100 0 0 S4 Not used Float glass X 0 0 100 Heatray reflective glass: KLS X 0 0 100 S5 Epikote 828 (4 parts) Float glassΔ 0 0 100 Heat ray reflective glass: KLS Δ 0 0 100 *¹◯: Elongation of80% or more, Δ: Elongation of less than 80%, X: Elongation of less than60% *²CF: Cohesion fracture, TCF: Thin-coat fracture, AF: Adhesionfracture

Examples S6 to S9, and Comparative Example S1

A mixture containing the polymer prepared in PRODUCTION EXAMPLE wasprepared for each of EXAMPLES S6 to S9, and COMPARATIVE EXAMPLE S1. Itwas composed of 100 parts of the polymer, 90 parts of a paraffin-basedprocess oil (Idemitsu Kosan, Diana Process Oil PS-32™), 30 parts oflimestone powder (Maruo Calcium, Snowlite SS™), 100 parts of colloidalcalcium carbonate (Shiraishi K. K., EDS-D10A™), 100 parts of talc (FujiTalc Kogyo, Talc LMR™), 6 parts of Na₂SO₄.10H₂O, 3 parts of nickeldimethyldithiocarbamate (Sanshin Kagaku Kogyo, Sandant NBC™) as a lightstabilizer, 3 parts of nickel[2,2′-thiobis(4-t-octylphenolate)]-n-butylamine (ACC, CYASORB UV-1084),1 part of antioxidant (Ciba-Geigy Japan, Irganox 1010™), 1 part ofultraviolet ray absorber (Ciba-Geigy Japan, Tinuvin 327™), 1 part oflight stabilizer (Sankyo, Sanol LS-770™), and 2 parts ofγ-glycidoxypropyltrimethoxysilane (Nippon Unicar, Silane coupling agentA-187™) as the silane coupling agent for the present invention and 4parts of γ-isocyanatepropyltriethoxysilane (Nippon Unicar, Silanecoupling agent Y-9030™), all parts by weight. It was also incorporatedwith china wood oil as the compound and component (V) for the presentinvention having an unsaturated group polymerizable on reacting oxygenin air, and dipentaerythritol penta- and hexa-acrylate as thephotopolymerizable compounds (TOAGOSEI, Aronix M-400™) in a quantitygiven in Table S2. Each mixture was well kneaded by a 3-paint roll unit,to produce the major ingredient for each example.

The curing agent was prepared by the following procedure: a mixturecomprising 10 parts of a paraffin-based process oil (Idemitsu Kosan,Diana Process Oil PS-32™), 20 parts of limestone powder (Maruo Calcium,Snowlite SS), 4 parts of a curing catalyst (NITTO KASEI, U-220™), and2.5 parts of carbon black (Mitsubishi Chemical, CB#30™), all parts byweight, was manually kneaded in a disposal cup and stirred 3 times at10,000 rpm each for 10 minutes by a homogenizer (Nihon Seiki SesakushoCo., Ltd., Excel Auto Homogenizer).

The H-shaped test piece was prepared in the same manner as in the above,except that it was cured under the conditions of 23° C.×7 days+50° C.×7days. The H-type tensile test piece, put in a Sunshine superlong-lifeweathermeter (Suga Shikenki, WEL-SUN-HC) with black panel temperaturekept at 63° C., was exposed to light emitted from sunshine carbon as thelight source in the weather resistance tester (SWOM) for a time given inTable S2, and taken out from the tester to be tested for tensileadhesion. Its weather-resistant adhesion was evaluated by comparing thetensile characteristics with fractured morphology. The results are givenin Table S2.

The H-shaped test piece was also tested for tensile adhesion forreference before it was tested for weather-resistance. The results aregiven in Table S3.

The composition prepared in each of EXAMPLES S6 to S9 was tested forcuring speed and resistance to weather in the same manner as in EXAMPLESS1 to S3. The results are also given in Table S7.

TABLE S2 Unsaturated compound capable Photopolymerizable SWOM ElongationFractured of reacting with oxygen in air Material Exposure at max.morphologies (%)*² (Addition rate) (Addition rate) Base materials timeload*¹ CF TCF AF COMPARATIVE Not used Not used Float glass 3000 X 0 0100 EXAMPLE S1 Heat ray reflective glass: KLS 500 x 100 0 0 EXAMPLE S6Not used AronixM400 Float glass 3000 X 50 50 0 (3 parts) Heat rayreflective glass: KLS 600 X 0 0 100 EXAMPLE S7 Not used AronixM400 Heatray reflective glass: KLS 500 ◯ 100 0 0 (6 parts) EXAMPLE S8 China woodoil Not used Float glass 3000 ◯ 100 0 0 (6 parts) Heat ray reflectiveglass: KLS 1000 ◯ 100 0 0 EXAMPLE S9 China wood oil AronixM400 Floatglass 3000 ◯ 100 0 0 (6 parts) (3 parts) Heat ray reflective glass: KLS1000 ◯ 100 0 0 *¹◯: Elongation of 80% or more, Δ: Elongation of lessthan 80%, X : Elongation of less than 60% *²CF: Cohesion fracture, TCF:Thin-coated fracture, AF: Adhesion fracture

TABLE S3 Unsaturated compound capable Photopolymerizable Fractured ofreacting with oxygen in air Material Elongation at morphologies (%)*²(Addition rate) (Addition rate) Base materials max. load^(*1) CF TCF AFCOMPARATIVE Not used Not used Float glass Δ 100 0 0 EXAMPLE S1 Heat rayreflective Δ 100 0 0 glass: KLS EXAMPLE S6 Not used AronixM400 Floatglass Δ 100 0 0 (3 parts) Heat ray reflective ◯ 100 0 0 glass: KLSEXAMPLE S7 Not used AronixM400 Heat ray reflective Δ 100 0 0 (6 parts)glass: KLS EXAMPLE S8 China wood oil(6 parts) Not used Float glass ◯ 1000 0 Heat ray reflective Δ 100 0 0 glass: KLS EXAMPLE S9 China wood oil(6parts) AronixM400 Float glass ◯ 100 0 0 (3 parts) Heat ray reflective ◯100 0 0 glass: KLS *¹◯: Elongation of 80% or more, Δ: Elongation of lessthan 80%, X: Elongation of less than 60% *²CF: Cohesion fracture, TCF:Thin-coat fracture, AF: Adhesion fracture

Reference Production Example

A 500 mL pressure-resistant glass reactor was charged, after it wasequipped with a 3-way cock and purged inside with nitrogen, 54 mL ofethyl cyclohexane (dried by molecular sieves 3A at least for a night),126 mL of toluene (also dried by molecular sieves 3A at least for anight) and 1.16 g (5.02 mmols) of p-DCC represented by the followingformula by a syringe.

Next, a pressure-resistant glass-made liquefied gas collecting tubeequipped with a needle valve and containing 56 mL of isobutylene monomerwas connected to the 3-way cock. Then the reactor for polymerization wasimmersed in a dry ice/ethanol bath kept at −70° C. to cool the solution,and evacuated to a vacuum. It was then charged with isobutylene monomerfrom the liquefied gas collecting tube by opening the needle valve, andreturned back to the normal pressure through introducing a nitrogen gasby handling the 3-way cock. The reactor was charged with 0.093 g (1.0mmol) of 2-methylpyridine and then with 1.65 mL (15.1 mmols) of titaniumtetrachloride, to initiate the polymerization. After a lapse of 70minutes, 1.22 g (10.8 mmols) of allyl trimethylsilane was added to thereactor to introduce the allyl group at the polymer terminal. After alapse of 120 minutes for the reaction, the reaction solution was washed4 times each with 200 mL of water, and the solvent was distilled off toobtain the isobutylene-based polymer with the allyl group at theterminal.

Next, 40 g of the isobutylene-based polymer with the allyl group at theterminal thus obtained was dissolved in 20 mL of n-heptane, and themixture was heated to around 70° C., to which 1.5 [eq/vinyl group] ofmethyl dimethoxysilane and 1×10⁻⁴ [eq/vinyl group] of a platinum/vinylsiloxane complex were added, for the hydrosilylation. The reaction wasfollowed by FT-IR. The olefin absorption at 1640 cm⁻¹ disappeared inaround 4 hours.

The reaction solution was concentrated under a vacuum, to produce theisobutylene polymer with the reactive silicon groups at both terminals,represented by the following formula:

The polymer yield was estimated from the quantity produced. It was alsoanalyzed for Mn and Mw/Mn by GPC, and the terminal structure bycomparing the intensities of the 300 MHz ¹H-NMR-analyzed resonancesignals of proton relevant to each structure (proton derived from theinitiator: 6.5 to 7.5 ppm, methyl proton bonded to the silicon atom,derived from the polymer terminal: 0.0 to 0.1 ppm, and methoxy proton:3.4 to 3.5 ppm) with each other.

The ¹H-NMR analysis was conducted using a Varian Gemini 300 (300 MHz for¹H) in CDCl₃.

The FT-IR analysis was conducted by an IR analyzer (Shimadzu IR-408),and GPC analysis was conducted with a Waters LC Module 1 as the liquidsending system and Shodex K-804 as the column. The molecular weight wasthe one relative to the polystyrene standard. The polymer thus preparedhad an Mn of 11,400, Mw/Mn of 1.23 and Fn (silyl) of 1.76, wherein thenumber-average molecular weight was as polystyrene, and the number ofthe terminal silyl functional group was that per 1 mol of isobutylenepolymer.

Reference Examples S1 to S5

A mixture containing the polymer prepared in REFERENCE PRODUCTIONEXAMPLE was prepared for each of REFERENCE EXAMPLES S1 to S5. It wascomposed of 100 parts of the polymer, 90 parts of a paraffin-basedprocess oil (Idemitsu Kosan, Diana Process Oil PS-32™), 30 parts oflimestone powder (Maruo Calcium, Snowlite SS™), 100 parts of colloidalcalcium carbonate (Shiraishi K. K., EDS-D10A™), 100 parts of talc (FujiTalc Kogyo, Talc LMR™), 6 parts of Na₂SO₄.10H₂O, 6 parts of china woodoil as the compound and component (V) for the present invention havingan unsaturated group polymerizable on reacting with oxygen in air, 3parts of dipentaerythritol penta- and hexa-acrylate as thephotopolymerizable compounds (TOAGOSEI, Aronix M-400™), and a tackifiergiven in Table S4 in a quantity also given in Table S4, all parts byweight. Each mixture was well kneaded by a 3-paint roll unit, to producethe major ingredient for each example.

The tackifiers used in REFERENCE EXAMPLES S3 to S5 wereγ-glycidoxypropyltrimethoxysilane (Nippon Unicar, Silane coupling agentA-187™) as the silane coupling agent and/orγ-isocyanatepropyltriethoxysilane (Nippon Unicar, Silane coupling agentY-9030™) in quantities given in Table S1. REFERENCE EXAMPLE S1 used notackifier, while REFERENCE EXAMPLE S2 used 4 parts by weight of an epoxyresin as the tackifier containing no hydrolyzable silicon group (exceptthe silane coupling agent) (Yuka Shell Epoxy, Epikote #828™).

The curing agent was prepared by the following procedure: a mixturecomprising 10 parts of a paraffin-based process oil (Idemitsu Kosan,Diana Process Oil PS-32™), 20 parts of limestone powder (Maruo Calcium,Snowlite SS™), 4 parts of a curing catalyst (NITTO KASEI, U-220™), and2.5 parts of carbon black (Mitsubishi Chemical, CB#30™), all parts byweight, was manually kneaded in a disposal cup and stirred 3 times at10,000 rpm each for 10 minutes by a homogenizer (Nihon Seiki SesakushoCo., Ltd., Excel Auto Homogenizer).

The test piece was prepared in accordance with JIS A-5758/1992 for thetensile adhesion test; 12 parts by weight of the major ingredient and 1part by weight of the curing agent were well kneaded, and the resultantmixture was put in the H-shape of glass base while breaking the bubblesin the composition by a spatula and cured in an oven under theconditions of 23° C.×1 day+50° C.×5 days for each composition. Thesubstrate for the H-type tensile test was of float glass (Koen-sha,designated by Japan Sealant Industry Association, 3 by 5 by 0.5 cm insize) in accordance with JIS A-5758/1992, or heat ray reflective glass(Central Glass, KLS™, 5 by 5 by 0.6 cm in size) coated with thermallyfused TiOx. Each of these H-shaped bases was washed withmethylethylketone (Wako-Junyaku, special grade) and wiped with cleancotton cloth, before it was filled with the composition. It was notcoated with a primer.

The H-shape test piece thus prepared for the tensile test was testedafter it was cured in the absence of primer by the method of testingtensile adhesion in accordance with JIS A-5758/1992. The test wasconducted at a tensile speed of 50 mm/minute by an autograph (Shimadzu,Autograph AG-2000A) in a constant-temperature chamber kept at 23° C. and50±10% RH, to evaluate adhesion in the absence of a primer by comparingthe tensile characteristics with fractured morphology. The results aregiven in Table S4, where the cohesion fracture (CF)/thin-coat fracture(TCF)/adhesion fracture (AF) ratio was determined by visual observationof the cross-sections of each tensile-tested piece.

Curing speed and resistance to weather were measured in REFERENCEEXAMPLES S3 to S5 in the same manner as in EXAMPLES S1 to S3. Theresults are given in Table S7.

TABLE S4 Tackifier Elongation at Fractured morphologies (%)*² (Additionrate) Base materials max. load*¹ CF TCF AF REFERENCE Not used Floatglass X 0 0 100 EXAMPLE S1 Heat ray reflective X 0 0 100 glass: KLSREFERENCE Epikote 828 Float glass X 0 0 100 EXAMPLE S2 (4 parts) Heatray reflective X 0 0 100 glass: KLS REFERENCE A-187 Float glass ◯ 100 00 EXAMPLE S3 (4 parts) Heat ray reflective ◯ 100 0 0 glass: KLSREFERENCE Y-9030 Float glass Δ 100 0 0 EXAMPLE S4 (4 parts) Heat rayreflective Δ 100 0 0 glass: KLS REFERENCE A-187 (2 parts) Float glass ◯100 0 0 EXAMPLE S5 Y-9030 (4 parts) Heat ray reflective Δ 100 0 0 glass:KLS *¹◯: Elongation of 80% or more, Δ: Elongation of less than 80%, X:Elongation of less than 60% *²CF: Cohesion fracture, TCF: Thin-coatfracture, AF: Adhesion fracture

Reference Examples S6 to S10

A mixture containing the polymer prepared in REFERENCE PRODUCTIONEXAMPLE was prepared for each of REFERENCE EXAMPLES S6 to S10 in thesame manner as in EXAMPLES S6 to S9 and COMPARATIVE EXAMPLE S1. It wascomposed of 100 parts of the polymer, 90 parts of a paraffin-basedprocess oil (Idemitsu Kosan, Diana Process Oil PS-32™), 30 parts oflimestone powder (Maruo Calcium, Snowlite SS™), 100 parts of colloidalcalcium carbonate (Shiraishi K. K., EDS-D10A™), 100 parts of talc (FujiTalc Kogyo, Talc LMR™), 6 parts of Na₂SO₄.10H₂O, 3 parts of nickeldimethyldithiocarbamate (Sanshin Kagaku Kogyo, Sandant NBC™) as thelight stabilizer, 3 parts of nickel[2,2′-thiobis(4-t-octylphenolate)]-n-butylamine (ACC, CYASORB UV-1084),1 part of antioxidant (Ciba-Geigy Japan, Irganox 1010™), 1 part ofultraviolet ray absorber (Ciba-Geigy Japan, Tinuvin 327™), 1 part oflight stabilizer (Sankyo, Sanol LS-770™), and 2 parts ofγ-glycidoxypropyltrimethoxysilane (Nippon Unicar, Silane coupling agentA-187™) as the silane coupling agent and 4 parts ofγ-isocyanatepropyltriethoxysilane (Nippon Unicar, Silane coupling agentY-9030™), all parts by weight. It was also incorporated with china woodoil as the compound and component (V) for the present invention havingan unsaturated group polymerizable on reacting with oxygen in air, anddipentaerythritol penta- and hexa-acrylate as the photopolymerizablecompounds (TOAGOSEI, Aronix M-400™) in a quantity given in Table S5.Each mixture was well kneaded by a 3-paint roll unit, to produce themajor ingredient for each example.

The curing agent was prepared by the following procedure: a mixturecomprising 10 parts of a paraffin-based process oil (Idemitsu Kosan,Diana Process Oil PS-32™), 20 parts of limestone powder (Maruo Calcium,Snowlite SS™), 4 parts of a curing catalyst (NITTO KASEI, U-22™), and2.5 parts of carbon black (Mitsubishi Chemical, CB#30™), all parts byweight, was manually kneaded in a disposal cup and stirred 3 times at10,000 rpm each for 10 minutes by a homogenizer (Nihon Seiki SesakushoCo., Ltd., Excel Auto Homogenizer).

The H-shaped test piece was prepared in the same manner as in the above,except that it was cured under the conditions of 23° C.×7 days+50° C.×7days. The H-type tensile test piece, put in a Sunshine superlong-lifeweathermeter (Suga Shikenki, WEL-SUN-HC) with black panel temperaturekept at 63° C., was exposed to light emitted from sunshine carbon as thelight source in the weather resistance tester (SWOM) for a time given inTable S5, and taken out from the tester to be tested for tensileadhesion. Its weather-resistant adhesion was evaluated by comparing thetensile characteristics with fractured morphology. The results are givenin Table S5.

The H-shaped test piece prepared as described above was also tested fortensile adhesion for reference before it was tested forweather-resistance. The results are also given in Table S6.

The composition prepared in each of REFERENCE EXAMPLES S7 to S10 wastested for curing speed and resistance to weather in the same manner asin EXAMPLES S1 to S3. The results are also given in Table S7.

TABLE S5 Unsaturated compound capable of reacting withPhotopolymerizable oxygen in air Material SWOM Elongation at Fracturedmorphologies (%)*² (Addition rate) (Addition rate) Base materialsExposure time max. load*¹ CF TCF AF REFERENCE Not used Not used Floatglass 3000 Δ 100 0 0 EXAMPLE S6 Heat ray reflective 500 Δ 0 0 100 glass:KLS REFERENCE Not used AronixM400 Float glass 3000 Δ 100 0 0 EXAMPLE S7(3 parts) Heat ray reflective 600 Δ 70 0 30 glass: KLS REFERENCE Notused AronixM400 Heat ray reflective 500 X 50 0 50 EXAMPLE S8 (6 parts)glass: KLS REFERENCE China wood oil(6 parts) Not used Float glass 3000 Δ100 0 0 EXAMPLE S9 Heat ray reflective 1000 Δ 100 0 0 glass: KLSREFERENCE China wood oil(6 parts) AronixM400 Float glass 3000 Δ 100 0 0EXAMPLE S10 (3 parts) Heat ray reflective 1000 Δ 100 0 0 glass: KLS *¹◯:Elongation of 80% or more, Δ: Elognation of less than 80%, X: Elongationof less than 60% *²CF: Cohesion fracture, TCF: Thin-coat fracture, AF:Adhesion fracture

TABLE S6 Unsaturated compound capable of reacting withPhotopolymerizable oxygen in air Material Elongation at Fracturedmorphologies (%)*² (Addition rate) (Addition rate) Base materials max.load*¹ CF TCF AF REFERENCE Not used Not used Float glass Δ 97 3 0EXAMPLE S6 Heat ray reflective Δ 100 0 0 glass: KLS REFERENCE Not usedAronixM400 Float glass Δ 98 2 0 EXAMPLE S7 (3 parts) Heat ray reflectiveX 98 2 0 glass: KLS REFERENCE Not used AronixM400 Heat ray reflective X100 0 0 EXAMPLE S8 (6 parts) glass: KLS REFERENCE China wood oil (6parts) Not used Float glass Δ 100 0 0 EXAMPLE S9 Heat ray reflective Δ100 0 0 glass: KLS REFERENCE China wood oil (6 parts) AronixM400 Floatglass X 100 0 0 EXAMPLE S10 (3 parts) Heat ray reflective X 100 0 0glass: KLS *¹◯: Elongation of 80% or more, Δ: Elongation of less than80%, X: Elongation of less than 60% *²CF: Cohesion fracture, TCF:Thin-coat fracture, AF: Adhesion fracture

TABLE S7 Curing speed* Resistance to weather EXAMPLE S1 ∘ No cracks ormolten portion observed EXAMPLE S2 ∘ No cracks or molten portionobserved EXAMPLE S3 ∘ No cracks or molten portion observed EXAMPLE S6 ∘No cracks or molten portion observed EXAMPLE S7 ∘ No cracks or moltenportion observed EXAMPLE S8 ∘ No cracks or molten portion observedEXAMPLE S9 ∘ No cracks or molten portion observed REFERENCE x Cracks ormolten EXAMPLE S3 portion observed REFERENCE x Cracks or molten EXAMPLES4 portion observed REFERENCE x Cracks or molten EXAMPLE S5 portionobserved REFERENCE x Cracks or molten EXAMPLE S7 portion observedREFERENCE x Cracks or molten EXAMPLE S8 portion observed REFERENCE xCracks or molten EXAMPLE S9 portion observed REFERENCE x Cracks ormolten EXAMPLE S10 portion observed *∘: Sufficiently serviceable, Δ:Tackiness remaining, x: Uncured

Examples T Series

The composition, the iodine value, the intrinsic viscosity [η] and themolecular weight distribution (Mw/Mn) of the copolymer rubber used ineach of EXAMPLES and COMPARATIVE EXAMPLES were determined by the methodsdescribed earlier.

Release-resisting force to silicone release paper, residual tackiness,tackiness, curing speed and weather resistance of the compositionsprepared in EXAMPLES and COMPARATIVE EXAMPLES were determined by thefollowing methods.

(1) Release-Resisting Force to Silicone Release Paper

The adhesive tape was prepared and put on a commercially availablesilicone release paper, to prepare the test piece. It was kept at 50° C.for 7, 14 or 21 days for the accelerated adhesion, taken out andreturned back to the normal temperature, and tested for itsrelease-resisting force, defined as the resistance of the adhesive tapewhen it was released by 180° from the silicone release paper at atensile speed of 300 mm/minute.

(2) Residual Tackiness

The adhesive tape was prepared and put on a commercially availablesilicone release paper, to prepare the test piece. It was left at 50°C., and the adhesive tape was released, to measure its tackiness. Theresidual tackiness is defined as the above tackiness relative to itsinitial tackiness, reported in percentage.

(3) Tackiness

The adhesive tape was prepared and put on a stainless steel plate, toprepare the test piece. It was left at 23° C. for 60 minutes, and testedfor its tackiness, defined as the release strength of the adhesive tapewhen it was released by 180° from the stainless steel plate at a tensilespeed of 300 mm/minute at 23° C.

(4) Curing Speed

The curable composition was cured at 23° C. and 50% RH for 24 hours in amold (20 by 80 by 5 mm in size).

The cured composition was released from the mold, and thickness of thecured portion of the composition was measured by a dial gauge of weakspring force to 0.1 mm. It was marked with ◯ when its thickness was 1 mmor more, and × when it was less than 1 mm.

Moreover, the time required for the composition to be cured under theconditions of 120° C. and 50% RH was measured. The composition wasmarked with ◯ when it was cured in less than 5 minutes, Δwhen it wascured in 5 to 10 minutes, and × when it was cured in more than 10minutes.

(5) Weather Resistance Test

The weather resistance test was conducted in accordance with JIS B-7753using a Sunshine Carbon Arc weatherometer, to determine resistance toweather:

<Testing Conditions>

-   Light irradiation/rainfall cycles: Irradiation for 120-   minutes/rainfall for 18 minutes-   Black panel temperature: 63±2° C.-   Tank inside temperature: 40±2° C.-   Total light irradiation time: 500 hours

Production Example T1

[Production of Silyl-containing ethylene/propylene/5-vinyl-2-norborneneRandom Copolymer Rubber (A-1)]

The three-component copolymerization was effected continuously in astainless steel polymerization reactor having an essential capacity of100 L, equipped with agitator blades (agitating rotation speed: 250rpm), wherein hexane, ethylene, propylene and 5-vinyl-2-norbornene werecontinuously supplied at 60 L, 2.5 kg, 4.0 kg and 380 g per hour,respectively, from the reactor side into the liquid phase, and hydrogen,VO(OEt)₂Cl and Al(Et)_(1.5)Cl_(1.5) as the catalysts at 700 L, 45 mmolsand 315 mmols per hour, respectively, also continuously.

The copolymerization effected under the above conditions produced theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A₀-1)in a form of uniform solution.

A small quantity of methanol was added to the polymer solution,continuously withdrawn from the reactor bottom, to terminate thepolymerization. The polymer was separated from the solvent bysteam-stripping the solution, and dried at 55° C. for 48 hours under avacuum.

The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber thusproduced contained ethylene at 68% bymol, and had an iodine value of 10(g/100 g), an intrinsic viscosity [η], as measured in decalin kept at135° C., of 0.2 dl/g, and Mw/Mn of 15.

Two % toluene solution (0.3 g) of chloroplatinic acid and 1.5 g ofmethyldimethoxysilane were added to 100 g of theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A₀-1),and they were allowed to react with each other at 120° C. for 2 hours.The excess methyldimethoxysilane and the solvent (toluene) weredistilled off from the effluent. This produced 101.5 g of the

-   -   ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber        (A-1) containing dimethoxymethylsilyl group (—SiCH₃(OCH₃)₂).

Production Example T2

Eight hundred grams of a polypropylene oxide (produced frompolypropylene glycol as the starting material) with allyl ether group at98% of the total terminals and having an average molecular weight ofaround 8,000, was charged in an agitator-equipped, pressure-resistantreactor, to which 20 g of methyldimethoxysilane was added, and then 0.34mL of a catalyst solution of chloroplatinic acid (8.9 g of H₂PtCl.6H₂Odissolved in 18 mL of isopropyl alcohol and 160 mL of tetrahydrofuran)was added, and they were allowed to react with each other at 80° C. for6 hours.

The unreacted silane was quantitatively analyzed by gas chromatographyand infrared analysis, to find the conversion rate. The resultsindicated that a polypropylene oxide with the following group at 84% ofits total terminals was produced:

Production Example T3

Tetra-n-butoxy zirconium, 38.3 g (0.1 mol) was dissolved in 88 g oftoluene, to which 10.0 g (0.1 mol) of acetylacetone was added slowlywith stirring. This produced tri-n-butoxy zirconium acetylacetonate,accompanied by generation of heat. The mixed toluene solution ishereinafter referred to as the PRODUCTION EXAMPLE 3 Catalyst.

Production Example T4

Tetra-n-butoxy zirconium, 38.3 g (0.1 mol) was dissolved in 87 g oftoluene, to which 20.0 g (0.2 mol) of acetylacetone was added slowlywith stirring. This produced di-n-butoxy zirconium bisacetylacetonate,accompanied by generation of heat. The mixed toluene solution ishereinafter referred to as the PRODUCTION EXAMPLE 4 Catalyst.

Production Example T5

Tetra-n-butoxy zirconium, 38.8 g (0.1 mol) was dissolved in 86 g oftoluene, to which 30.0 g (0.3 mol) of acetylacetone was added slowlywith stirring. This produced di-n-butoxy zirconium trisacetylacetonate,accompanied by generation of heat. The mixed toluene solution ishereinafter referred to as the PRODUCTION EXAMPLE 5 Catalyst.

Production Example T6

n-Butyl acrylate, 128 g (1.0 mol), 3.48 g (0.015 mol) ofγ-methacryloxypropylmethyldimethoxysialne, 2.46 g (0.015 mol) ofγ-mercaptopropylmethyldimethoxysilane and 0.25 g ofα,α′-azobisisobutylonitrile were mixed and dissolved, and 30 g of theresultant mixed solution was charged in a 300 mL four-mouthed flaskpurged with nitrogen gas and slowly heated with stirring in an oil bathkept at 70° C. This soon started the polymerization, which wasaccompanied by generation of heat and thickening of the reactionsolution. The remaining mixed solution was slowly added with stirring tothe reaction solution dropwise over 2.5 hours via the drip-feed funnel.The reaction solution was continuously stirred for 1 hour aftercompletion of the addition of the mixed solution, to complete thepolymerization. This produced a colorless, transparent, viscoussubstance having a viscosity of 350P (23° C.) at a polymerization rateof 97%.

Examples T1 to T9

The silyl-containing ethylene/propylene/5-vinyl-2-norbornene randomcopolymer rubber (A-1), prepared in PRODUCTION EXAMPLE T1, 100 parts byweight, was incorporated with 80 parts by weight of the tackifier resingiven in Table T1, to prepare the toluene solution containing the solidsat 80% for each of EXAMPLES T1 to T9.

The solution was incorporated with the curing catalyst given in TableT1, and the resultant composition was spread over a 25 μm thickpolyester substrate (Toray Industries, Lumirror Film) by a coater to athickness of 25 μm (on a dry basis), and cured at 120° C. for 0.5 to 5minutes by a drier.

The resultant adhesive tape was measured for its releasability from asilicone release paper (Soken Industries, Inc., EK-130R). Its curingspeed and resistance to weather were evaluated by the curing speed andweather resistance tests conducted according to the methods describedearlier. The results are given in Table T1.

In Table T1, YS Polyster T-115 and YS Polyster S-145 are terpenephenolic resins (Yasuhara Yushi Kogyo), and Stepelite Ester 7 is ahydrogenated rosin ester resin (Hercules). Zr(acac)₄ in Table T1 iszirconium tetraacetylacetonate.

TABLE T1 Exfoliation resisting force Curing Curing catalysts Curing[g/cm] Adhesive Residual adhesion rate [%] speed at EX- Content Speed50° C. 50° C. 50° C. force 50° C. 50° C. 50° C. room Resistance AM-Tackifier (parts by at × × × (initial) × × × temper- to weather PLESresin Types weight) 120° C. 7 days 14 days 21 days [g/cm] 7 days 14 days21 days ature *4 T1 YS PRODUCTION 5 ◯ 4 3 2 430 94 96 92 ◯ ⊚ PolysterEXAMPLE 3 T-115 Catalyst *1 T2 YS PRODUCTION 5 ◯ 3 5 3 440 92 94 94 ◯ ⊚Polyster EXAMPLE 4 T-115 Catalyst *2 T3 YS PRODUCTION 5 ◯ 4 4 3 420 9799 98 ◯ ⊚ Polyster EXAMPLE 5 T-115 Catalyst *3 T4 YS PRODUCTION 5 ◯ 4 43 800 98 99 96 ◯ ⊚ Polyster EXAMPLE 5 S-145 Catalyst *3 T5 StepelitePRODUCTION 5 ◯ 2 2 3 220 90 88 87 ◯ ⊚ Ester 7 EXAMPLE 5 Catalyst *3 T6YS Zr(acac)₄ 5 ◯ 4 3 2 410 86 84 82 ◯ ⊚ Polyster T-115 T7 YS (n-BuO)₄Zr5 ◯ 5 5 6 400 87 85 86 ◯ ⊚ Polyster T-115 T8 YS Al(acac)₃ 5 ◯ 3 4 4 39090 88 87 ◯ ⊚ Polyster T-115 T9 YS Diisopropoxy Al 5 ◯ 6 6 5 405 88 90 90◯ ⊚ Polyster ethylacetoacetate T-115 *1: As (n-BuO)₃Zr(acac), *2: As(n-BuO)₂Zr(acac)₂, *3: As (n-BuO)Zr(acac)₃, *4: Evaluation standards forresistance to weather, ⊚: No change observed, ◯: Cracks or moltenportion slightly observed, Δ: Cracks or molten portion observed, and X:Cracks or molten portion extensively observed

Reference Examples T1 to T9

The polyalkylene oxide containing the hydrolysable silicon group,prepared in PRODUCTION EXAMPLE T2, 100 parts by weight was incorporatedwith 80 parts by weight of the tackifier resin given in Table T2, toprepare the toluene solution containing the solids at 80% for each ofREFERENCE EXAMPLES T1 to T9.

The solution was incorporated with the curing catalyst given in TableT2, and the resultant composition was spread over a 25 μm thickpolyester substrate (Toray Industries, Lumirror Film) by a coater to athickness of 25 μm (on a dry basis), and cured at 120° C. for 1 to 19minutes by a drier.

The resultant adhesive tape was measured for its releasability from asilicone release paper (Soken Industries, Inc., EK-130R). Its curingspeed and resistance to weather were evaluated by the curing speed andweather resistance tests conducted according to the methods describedearlier. The results are given in Table T2.

In Table T2, YS Polyster T-115 and YS Polyster S-145 are terpenephenolic resins (Yasuhara Yushi Kogyo), and Stepelite Ester 7 is ahydrogenated rosin ester resin (Hercules).

Zr(acac)₄ in Table T2 is zirconium tetraacetylacetonate.

Comparative Examples T1 to T3

The adhesive tape was prepared for each of COMPARATIVE EXAMPLES T1 to T3in the same manner as in COMPARATIVE EXAMPLE T1, except that theorganotin compound as the curing catalyst was used, as shown in TableT2, and measured for its releasability. Its curing speed and resistanceto weather were evaluated by the curing speed and weather resistancetests conducted according to the methods described earlier. The resultsare given in Table T2.

TABLE T2 Curing catalysts Exfoliation resisting force Content Curing[g/cm] Adhesive Residual adhesion rate [%] Resis- (parts Speed 50° C.50° C. 50° C. force 50° C. 50° C. 50° C. tance to Tackifier by at × × ×(initial) × × × Curing weather resin Types weight) 120° C. 7 days 14days 21 days [g/cm] 7 days 14 days 21 days speed *4 REF- YS PRODUCTION 5◯ 3 3 2 360 90 92 90 ◯ Δ ERECE Polyster EXAMPLE 3 EXAM- T-115 Catalyst*1 PLE T1 REF- YS PRODUCTION 5 ◯ 2 4 3 365 89 92 92 ◯ Δ ERECE PolysterEXAMPLE 4 EXAM- T-115 Catalyst *2 PLE T2 REF- YS PRODUCTION 5 ◯ 2 3 3360 94 97 95 ◯ Δ ERECE Polyster EXAMPLE 5 EXAM- T-115 Catalyst *3 PLE T3REF- YS PRODUCTION 5 ◯ 3 3 4 750 92 93 91 ◯ X to Δ ERECE PolysterEXAMPLE 5 EXAM- S-145 Catalyst *3 PLE T4 REF- Stepelite PRODUCTION 5 ◯ 33 3 160 84 80 78 ◯ Δ ERECE Ester 7 EXAMPLE 5 EXAM- Catalyst *3 PLE T5REF- YS Zr(acac)₄ 5 ◯ 2 3 3 360 74 78 74 ◯ Δ ERECE Polyster EXAM- T-115PLE T6 REF- YS (n-BuO)₄ 5 Δ 4 4 5 370 77 76 75 ◯ X ERECE Polyster ZrEXAM- T-115 PLE T7 REF- YS Al(acac)₃ 5 ◯ 2 3 3 350 80 78 81 ◯ Δ ERECEPolyster EXAM- T-115 PLE T8 REF- YS Diisopropoxy 5 ◯ 5 6 6 375 78 80 80◯ Δ ERECE Polyster Al ethylaceto- EXAM- T-115 acetate PLE T9 COM- YSDibutyl tin 5 X 260 Im- Im- 365 50 — — X X PAR- Polyster dilaurate meas-meas- ATIVE T-115 urable urable EXAM- PLE T1 COM- YS Dibutyl tin 5 ◯ 250Im- Im- 360 34 — — ◯ X PAR- Polyster monononyl meas- meas- ATIVE T-115phenolate urable urable EXAM- PLE T2 COM- YS Dibutyl tin 5 ◯ 240 Im- Im-355 32 — — ◯ X PAR- Polyster dimethoxide meas- meas- ATIVE T-115 urableurable EXAM- PLE T3 *1: As (n-BuO)₃Zr(acac), *2: As (n-BuO)₂Zr(acac)₂,*3: As (n-BuO)Zr(acac)₃, *4: Evaluation standards for resistance toweather, ⊚: No change observed, ◯: Cracks or molten portion slightlyobserved, Δ: Cracks or molten portion observed, and X: Cracks or moltenportion extensively observed

As shown in Table T2, the adhesive tape with the composition prepared ineach of REFERENCE EXAMPLES T1 to T9 has better releasability from thesilicone release paper than that with the composition prepared in eachof COMPARATIVE EXAMPLES T1 to T3.

Reference Examples T10 to T15

The acrylate copolymer containing the hydrolysable silicon group,prepared in PRODUCTION EXAMPLE T6, 100 parts by weight, was incorporatedwith 50 parts by weight of YS Polyster T-115, to prepare the toluenesolution containing the solids at 80% for each of REFERENCE EXAMPLES T10to T15.

The solution was incorporated with the curing catalyst given in TableT3, and the resultant composition was spread over a 25 μm thickpolyester substrate (Toray Industries, Lumirror Film) to a thickness of25 μm (on a dry basis), and cured at 120° C. for 3 minutes to preparethe adhesive tape.

The resultant adhesive tape was measured for its releasability from asilicone release paper in the same manner as in COMPARATIVE EXAMPLE T1.Its curing speed and resistance to weather were evaluated by the curingspeed and weather resistance tests conducted according to the methodsdescribed earlier. The results are given in Table T3.

Comparative Examples T4 and T5

The adhesive tape was prepared for each of COMPARATIVE EXAMPLES T4 andT5 in the same manner as in REFERENCE EXAMPLE T10, except that thecuring catalyst was replaced by the organotin compound shown in TableT3, and measured for its releasability. Its curing speed and resistanceto weather were evaluated by the curing speed and weather resistancetests conducted according to the methods described earlier. The resultsare given in Table T3.

TABLE T3 Exfoliation resisting force Curing catalysts [g/cm] Residualadhesion rate [%] Content 50° C. 50° C. 50° C. Adhesive 50° C. 50° C.50° C. Curing speed Resistance to (parts by × × × force (initial) × × ×[ordinary weather Types weight) 7 days 14 days 21 days [g/cm] 7 days 14days 21 days temperature] *4 REFERENCE PRODUCTION 5 3 3 3 320 84 80 81 ◯Δ to X EXAMPLE T10 EXAMPLE 3 Catalyst*1 REFERENCE PRODUCTION 5 3 2 3 33078 79 81 ◯ Δ to X EXAMPLE T11 EXAMPLE 4 Catalyst*2 REFERENCE PRODUCTION5 2 3 3 315 82 82 80 ◯ Δ to X EXAMPLE T12 EXAMPLE 5 Catalyst*3 REFERENCEZr(acac)₄ 5 3 4 4 340 77 76 77 ◯ Δ to X EXAMPLE T13 REFERENCE Al(acac)₃5 4 6 5 355 79 79 80 ◯ Δ EXAMPLE T14 REFERENCE Diisopropoxy Al 5 3 4 4345 80 81 81 ◯ Δ EXAMPLE T15 ethylacetoacetate COMPARATIVE Dibutyl tin 5120 250 — 360 45 33 — ◯ X EXAMPLE T4 dilaurate COMPARATIVE Dibutyl tinmono- 5 65 170 — 355 38 24 — ◯ X EXAMPLE T5 nonylpheonolate *1: As(n-BuO)₃Zr(acac), *2: As (n-BuO)₂Zr(acac)₂, *3: As (n-BuO)Zr(acac)₃, *4:Evaluation standards for resistance to weather, ⊚: No change observed,◯: Cracks or molten portion slightly observed, Δ: Cracks or moltenportion observed, and X: Cracks or molten portion extensively observed

Examples U Series

The composition, the iodine value, the intrinsic viscosity [η] and themolecular weight distribution (Mw/Mn) of the copolymer rubber used ineach of EXAMPLES and REFERENCE EXAPLES were determined by the methodsdescribed earlier.

The gel fraction measurement and weather resistance tests in EXAMPLESand REFERENCE EXAMPLES were conducted according to the followingmethods.

(1) Gel Fraction Measurement Test

The cured coating film was immersed in acetone kept at 20° C. for 24hours, to find the weight of its undissolved portion relative to thefilm weight before the test. It was marked with × when it was less than60%, Δ when it was 60% or more but less than 80%, ◯ when it was 80% ormore but less than 90%, and ⊚ when it was 90% or more.

(2) Weather Resistance Test

The weather resistance test was conducted in accordance with JIS B-7753using a Sunshine Carbon Arc weatherometer, to determine resistance toweather:

<Testing Conditions>

-   Light irradiation/rainfall cycles: Irradiation for 120-   minutes/rainfall for 18 minutes-   Black panel temperature: 63±2° C.-   Tank inside temperature: 40±2° C.-   Total light irradiation time: 250 hours    <Evaluation Standards for Resistance to Weather>-   ◯: No cracks or molten portion observed on one side of the tested    piece-   Δ: Cracks or molten portion observed slightly on one side of the    tested piece-   ×: Cracks or molten portion observed on one side of the tested piece

Example U

[Production of Silyl-containing ethylene/propylene/5-vinyl-2-norborneneRandom Copolymer Rubber (A-1)]

The three-component copolymerization was effected continuously in astainless steel polymerization reactor having an essential capacity of100 L, equipped with agitator blades (agitating rotation speed: 250rpm), wherein hexane, ethylene, propylene and 5-vinyl-2-norbornene werecontinuously supplied at 60 L, 2.5 kg, 4.0 kg and 380 g per hour,respectively, from the reactor side into the liquid phase, and hydrogen,VO(OEt)₂Cl and Al(Et)_(1.5)Cl_(1.5) as the catalysts at 700 L, 45 mmolsand 315 mmols per hour, respectively, also continuously.

The copolymerization effected under the above conditions produced theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A₀-1)in a form of uniform solution.

A small quantity of methanol was added to the polymer solution,continuously withdrawn from the reactor bottom, to terminate thepolymerization. The polymer was separated from the solvent bysteam-stripping the solution, and dried at 55° C. for 48 hours under avacuum.

The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber(A₀-1) thus produced contained ethylene at 68% by mol, and had an iodinevalue of 10 (g/100 g), an intrinsic viscosity [η], as measured indecalin at 135° C., of 0.2 dl/g, and Mw/Mn of 15.

Two % toluene solution (0.3 g) of chloroplatinic acid and 1.5 g ofmethyldimethoxysilane were added to 100 g of theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A₀-1),and they were allowed to react with each other at 120° C. for 2 hours.The excess methyldimethoxysilane and the solvent (toluene) weredistilled off from the effluent. This produced 101.5 g of the

-   -   ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber        (A-1) containing dimethoxymethylsilyl group (—SiCH₃(OCH₃)₂).

Reference Example U1

A solution of 2 g of azobisisobutylonitrile dissolved in 30 g ofstyrene, 16 g of allyl methacrylate, 20 g of methyl methacrylate, 19 gof n-butyl methacrylate, 14 g of butyl acrylate, 4 g of maleic anhydrideand 2 g of n-dodecylmercaptan was added dropwise in 90 g of xylene asthe solvent kept at 90° C., and these compounds were allowed to reactwith each other for 10 hours, to obtain the vinyl-based polymer having amolecular weight of 8,000 and containing an allyl type unsaturatedgroup. The polymer had absorptions relevant to the carbon-carbon doublebond and acid anhydride at 1648 and 1780 cm⁻¹, respectively, in theinfrared absorption spectral pattern. The polymer solution was distilledunder a vacuum to remove 40 g of the solvent.

A solution of 1.5 g of trimethoxysilane and 0.0005 g of chloroplatinicacid dissolved in isopropanol was added to 16 g of the vinyl-basedpolymer having an allyl type unsaturated group, and they were allowed toreact with each other at 90° C. for 6 hours in a sealed system. Thereaction product had no infrared absorption at 1648 cm⁻¹ in the infraredabsorption spectral pattern, from which it was judged thatsilyl-containing vinyl-based polymer was produced.

Reference Example U2

A solution of 2 g of azobisisobutylonitrile dissolved in 30 g ofstyrene, 22 g of γ-methacryloxypropyltrimethoxysilane, 22 g of methylmethacrylate, 15 g of n-butyl methacrylate and 18 g of butyl acrylatewas added dropwise in 70 g of xylene as the solvent kept at 90° C., andthese compounds were allowed to react with each other for 10 hours, toobtain the silyl-containing vinyl-based polymer having a molecularweight of 16,000.

Reference Example U3

A solution of 2 g of azobisisobutylonitrile dissolved in 30 g ofstyrene, 22 g of γ-methacryloxypropyltrimethoxysilane, 22 g ofmethylmethacrylate, 15 g of n-butyl methacrylate, 18 g of butyl acrylateand 2 g of n-dodecylmercaptan was added dropwise in 70 g of xylene asthe solvent kept at 90° C., and these compounds were allowed to reactwith each other for 10 hours, to obtain the silyl-containing vinyl-basedpolymer having a molecular weight of 9,000.

Reference Example U4

A solution of 2 g of azobisisobutylonitrile dissolved in 30 g ofstyrene, 22 g of γ-methacryloxypropyltrimethoxysilane, 52 g ofmethylmethacrylate, 15 g of n-butyl methacrylate, 18 g of butylacrylate, 4 g of acrylamide, 10 g of n-butanol and 4 g ofn-dodecylmercaptan was added dropwise in 70 g of xylene as the solventkept at 70° C., and these compounds were allowed to react with eachother for 10 hours, to obtain the silyl-containing vinyl-based polymerhaving a molecular weight of 6,000.

Reference Example U5

A solution of 2 g of azobisisobutylonitrile dissolved in 30 g ofstyrene, 22 g of γ-methacryloxypropyltrimethoxysilane, 22 g of methylmethacrylate, 15 g of n-butyl methacrylate, 18 g of butyl acrylate, 4 gof 2-hydroxyethyl methacrylate and 4 g of n-dodecylmercaptan was addeddropwise in 70 g of xylene as the solvent kept at 90° C., and thesecompounds were allowed to react with each other for 10 hours, to obtainthe silyl-containing vinyl-based polymer having a molecular weight of6,000.

Reference Example U6

The silyl-containing vinyl-based polymer having a molecular weight of5,000 was obtained in the same manner as in REFERENCE EXAMPLE U4, exceptthat 4 g of n-dodecylmercaptan and 4 g of 2-hydroxyethyl methacrylate inREFERENCE EXAMPLE U5 were replaced by 6 g of n-dodecylmercaptan, 4 g ofacrylamide, 2 g of maleic anhydride and 10 g of n-butanol.

The resin solution obtained in each of EXAMPLE U and REFERENCE EXAMPLESU1 to U6 was incorporated with the additive(s) and the curingcatalyst(s) given in Table U1, and diluted with xylene to the resinviscosity (Ford cup viscosity: 15 seconds), to measure the pot lifebefore it was skinned or gelled under open conditions.

Moreover, the gel fraction measurement test was conducted in accordancewith the above-described method for the mixture of the resin solution,obtained in each of EXAMPLE U and REFERENCE EXAMPLES U1 to U6, and theadditive(s) and the curing catalyst(s) given in Table U1.

The mixture was left in a glass petri dish, 2 cm in diameter and 1.5 cmdeep, to be cured at room temperature, and the cured composition wasmeasured for resistance to weather by the above-described method.

The results are given in Table U1.

TABLE U1 REFERENCE REFERENCE REFERENCE REFERENCE EXAMPLE U3 REFERENCEEXAMPLE U5 REFERENCE EXAMPLE U EXAMPLE U1 EXAMPLE U2 (1) (2) EXAMPLE U4(1) (2) EXAMPLE U6 Curing catalyst [parts by weight] Stann JF-9B (*1)  3 3  3 2.4 — 3 — —  3 Phthalic aid — — — — — — —  1 — Dibutyl tindilaurate — — — — — —  3  3 — Tin octylate — — — 0.6  1 — — — — Additive[parts by weight] Methanol 10 10 10 — — — 10 10 10 Tetraethyl 10 10 — 10 10 — 10 10 10 orthosilicate Trimethyl — — — — — — — —  1orthoformate Pot life under open 10 hrs≦ 10 hrs≦ 10 hrs≦ 10 hrs≦Skinning 10 hrs≦ Skinning 10 hrs≦ 10 hrs≦ conditions in 3 hrs in 3 hrsEvaluation of gel ⊚ X Δ X ◯ Δ ◯ X Δ fraction Evaluation of ◯ Δ Δ Δ X Δ XΔ X resistance to weather (*1) Stann JF-98: Stabilizer for vinylchloride (Sankyo Organic Chemicals, Ltd.) Chemical formula of the majoringredient: (n-C₄H₉—)₂Sn(—SCH₂COOR)₂, (R: C4 to C12) (*2) Parts byweight for the curing catalyst and additive are based on 100 parts byweight of the resin

Examples V Series

The composition, the iodine value, the intrinsic viscosity [η] and themolecular weight distribution (Mw/Mn) of the copolymer rubber used ineach of EXAMPLES and COMPARATIVE EXAPLES were determined by the methodsdescribed earlier.

Production Example V1

Production of Silyl-containing ethylene/propylene/5-vinyl-2-norborneneRandom Copolymer Rubber (A-1)

The three-component copolymerization was effected continuously in astainless steel polymerization reactor having an essential capacity of100 L, equipped with agitator blades (agitating rotation speed: 250rpm), wherein hexane, ethylene, propylene and 5-vinyl-2-norbornene werecontinuously supplied at 60 L, 2.5 kg, 4.0 kg and 380 g per hour,respectively, from the reactor side into the liquid phase, and hydrogen,VO(OEt)₂Cl and Al(Et)_(1.5)Cl_(1.5) as the catalysts at 700 L, 45 mmolsand 315 mmols per hour, respectively, also continuously.

The copolymerization effected under the above conditions produced theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A₀-1)in a form of uniform solution.

A small quantity of methanol was added to the polymer solution,continuously withdrawn from the reactor bottom, to terminate thepolymerization. The polymer was separated from the solvent bysteam-stripping the solution, and dried at 55° C. for 48 hours under avacuum.

The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber(A₀-1) thus produced contained ethylene at 68% by mol, and had an iodinevalue of 10 (g/100 g), an intrinsic viscosity [η], as measured indecalin at 135° C., of 0.2 dl/g, and Mw/Mn of 15.

Two % toluene solution (0.3 g) of chloroplatinic acid and 1.5 g ofmethyldimethoxysilane were added to 100 g of theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A₀-1),and they were allowed to react with each other at 120° C. for 2 hours.The excess methyldimethoxysilane and the solvent (toluene) weredistilled off from the effluent. This produced 101.5 g of theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1)containing dimethoxymethylsilyl group (—SiCH₃(OCH₃)₂).

Production Example V2

[Production of Saturated Hydrocarbon-Based Polymer (D-1)]

A uniformly mixed solution of 560 mL of methylene chloride, 1,160 mL ofn-hexane, 940 mg of a-methylpyridine and 22 g of p-dicumyl chloride, alldried, was formed in a four-mouthed flask equipped with an agitator andnitrogen line and cooled to −70° C., in which 570 mL of isobutylenemonomer was charged under a vacuum through a molecular sieves tube.

A polymerization catalyst solution (comprising 14 mL of titaniumtetrachloride and 80 mL of methylene chloride) cooled beforehand wasadded all at once to the above reaction solution, kept at −70° C., withstirring to initiate the polymerization reaction. The reaction solutionwas heated to −54° C., and then cooled to −70° C. in about 17 minutes.

About 20 minutes after the polymerization was initiated, 132 g of1,9-decadiene was added to the reaction solution, and continuouslystirred at −70° C. for 4 hours.

The yellowy turbid reaction solution thus produced was put in 3 L ofwarm water (around 45° C.) and stirred for around 2 hours. Then, theorganic layer was separated, and washed with pure water 3 times. Theresultant colorless, transparent organic layer was concentrated under avacuum, to obtain approximately 400 g of the isobutylene oligomer withvinyl groups at both terminals.

Next, 400 g of the isobutylene oligomer with vinyl groups at bothterminals was dissolved in 200 mL of n-heptane. The resultant solutionwas heated to around 70° C., to which 1.5 [eq/vinyl group] of methyldimethoxysilane and 1×10⁻⁴[eq/vinyl group] of a platinum/vinyl siloxanecomplex were added, for the hydrosilylation. The reaction was followedby FT-IR. The olefin absorption at 1640 cm⁻¹ disappeared in around 4hours.

The reaction solution was concentrated under a vacuum, to obtain thetarget isobutylene oligomer (D-1) having the reactive silicon group atboth terminals.

[Structural Formula]

Production Example V3

[Production of Saturated Hydrocarbon-Based Polymer (D-2)]

The same procedure as used for PRODUCTION EXAMPLE V2 was repeated inPRODUCTION EXAMPLE V3, except that 1,9-decadiene was replaced by 24 g ofallylmethylsilane, to obtain the isobutylene oligomer (D-2) of partlydifferent production intermediate structure.

[Structural Formula]

Production Example V4

[Production of Saturated Hydrocarbon-Based Polymer (D-3)]

A uniformly mixed solution of 560 mL of methylene chloride, 1,160 mL ofn-hexane, 940 mg of α-methylpyridine and 22 g of p-dicumyl chloride, alldried, was formed in a four-mouthed flask equipped with an agitator andnitrogen line, and cooled to −70° C., in which 570 mL of isobutylenemonomer was charged under a vacuum through a molecular sieves tube.

A polymerization catalyst solution (comprising 14 mL of titaniumtetrachloride and 80 mL of methylene chloride) cooled beforehand wasadded all at once to the above reaction solution, kept at −70° C., withstirring to initiate the polymerization reaction. The reaction solutionwas heated to −54° C., and then cooled to −70° C. in about 17 minutes.The reaction solution was continuously stirred for around 60 minutesafter the polymerization was initiated. The yellowy turbid reactionsolution thus produced was put in 3 L of warm water (around 45° C.) andstirred for around 2 hours. Then, the organic layer was separated, andwashed with pure water 3 times. The resultant colorless, transparentorganic layer was concentrated under a vacuum, to obtain approximately400 g of the isobutylene oligomer with chlorous groups at bothterminals.

Then, the isobutylene oligomer was continuously heated at 170° C. undera vacuum for 2 hours for the thermal dehydrochlorination reaction, toobtain the isobutylene oligomer with isopropenyl groups at bothterminals.

Next, 400 g of the isobutylene oligomer with isopropenyl groups at bothterminals, prepared above, was dissolved in 200 mL of n-heptane. Theresultant solution was heated in a pressure vessel to around 100° C., towhich 1.5 [eq/vinyl group] of methyl dichlorosilane and 1×10⁻⁴[eq/vinylgroup] of a platinum/vinyl siloxane complex were added, for thehydrosilylation. The reaction was followed by FT-IR. The olefinabsorption at 1640 cm⁻¹ disappeared in around 10 hours. The reactionsolution was cooled to 60° C., to which an excess quantity of methanolover methyl dichlorosilane was added, and the mixture was stirred foraround 4 hours, to complete the methoxylation. The reaction solution wasconcentrated under a vacuum, to obtain the target isobutylene oligomer(D-3) having the structure with the reactive silicon group at bothterminals.

[Structural Formula]

Example V1

A mixture containing the polymer (A-1) prepared in PRODUCTION EXAMPLE V1as the silane-modified ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1) was prepared. It was composed of 100 parts of thepolymer rubber (A-1), 120 parts of calcium carbonate (Shiraishi K. K.,CCR™), 90 parts of a paraffin-based process oil (Idemitsu Kosan, DianaProcess Oil PS-32™) as the plastcizer, 30 parts of titanium dioxide, 5parts of sodium bisulfate, and 3 parts of dibutyl tin bisacetylacetonateas the curing catalyst (H8), all parts by weight. These components wereuniformly kneaded to obtain the curable composition.

Curability (tack-free time) of the resultant composition was measured inaccordance with JIS A-5758. It was cured in 16 minutes.

Dibutyl tin bisacetylacetonate

Comparative Example V1

The curable composition was prepared in the same manner as in EXAMPLEV1, except that the curing catalyst (H8) was replaced by tin dioctylate.

Curability (tack-free time) of the resultant composition was measured inaccordance with JIS A-5758. It was not cured even after a lapse of 700minutes or more.

Tin dioctylate

Reference Example V1

A mixture containing the polymer (D-1) prepared in PRODUCTION EXAMPLE V2as the saturated hydrocarbon-based polymer component was prepared. Itwas composed of 100 parts of the polymer (D-1), 120 parts of calciumcarbonate (Shiraishi K. K., CCR™), 90 parts of a paraffin-based processoil (Idemitsu Kosan, Diana Process Oil PS-32™) as the plastcizer, 30parts of titanium dioxide, 5 parts of sodium bisulfate, and 3 parts ofdibutyl tin bisacetylacetonate as the curing catalyst (H8), all parts byweight. These components were uniformly kneaded to obtain the curablecomposition.

Curability (tack-free time) of the resultant composition was measured inaccordance with JIS A-5758. It was cured in 25 minutes.

Reference Example V2

A mixture containing the polymer (D-2) prepared in PRODUCTION EXAMPLE V3as the saturated hydrocarbon-based polymer component was prepared. Itwas composed of 100 parts of the polymer (D-2), 120 parts of calciumcarbonate (Shiraishi K. K., CCR™), 90 parts of a paraffin-based processoil (Idemitsu Kosan, Diana Process Oil PS-32™) as the plastcizer, 30parts of titanium dioxide, 5 parts of sodium bisulfate, and 3 parts ofdibutyl tin bisacetylacetonate as the curing catalyst (H8), all parts byweight. These components were uniformly kneaded to obtain the curablecomposition.

Curability (tack-free time) of the resultant composition was measured inaccordance with JIS A-5758. It was cured in 30 minutes.

Reference Example V3

A mixture containing the polymer (D-3) prepared in PRODUCTION EXAMPLE V4as the saturated hydrocarbon-based polymer component was prepared. Itwas composed of 100 parts of the polymer (D-3), 120 parts of calciumcarbonate (Shiraishi K. K., CCR™), 90 parts of a paraffin-based processoil (Idemitsu Kosan, Diana Process Oil PS-32™) as the plastcizer, 30parts of titanium dioxide, 5 parts of sodium bisulfate, and 3 parts ofdibutyl tin bisacetylacetonate as the curing catalyst (H8), all parts byweight. These components were uniformly kneaded to obtain the curablecomposition.

Curability (tack-free time) of the resultant composition was measured inaccordance with JIS A-5758. It was cured in 30 minutes.

Reference Example V4

The curable composition was prepared in the same manner as in REFERENCEEXAMPLE V1, except that the polymer (D-1) prepared in PRODUCTION EXAMPLEV2 as the saturated hydrocarbon-based polymer was incorporated with tindioctylate in place of the curing catalyst (H8).

Curability (tack-free time) of the resultant composition was measured inaccordance with JIS A-5758. It was not cured even after a lapse of 700minutes or more.

Reference Example V5

The curable composition was prepared in the same manner as in REFERENCEEXAMPLE V2, except that the polymer (D-2) prepared in PRODUCTION EXAMPLEV3 as the saturated hydrocarbon-based polymer was incorporated with tindioctylate in place of the curing catalyst (H8).

Curability (tack-free time) of the resultant composition was measured inaccordance with JIS A-5758. It was not cured even after a lapse of 700minutes or more.

Reference Example V6

The curable composition was prepared in the same manner as in REFERENCEEXAMPLE V3, except that the polymer (D-3) prepared in PRODUCTION EXAMPLEV4 as the saturated hydrocarbon-based polymer was incorporated with tindioctylate in place of the curing catalyst (H8).

Curability (tack-free time) of the resultant composition was measured inaccordance with JIS A-5758. It was not cured even after a lapse of 700minutes or more.

The curing speed test and accelerated weather resistance test wereconducted by the following methods for EXAMPLES and COMPARATIVEEXAMPLES.

(1) Curing Speed Test

The curable composition was cured under the conditions of 23° C. and 50%RH for 24 hours in a mold, 20 by 80 by 5 mm in size.

Next, the cured product was released from the mold, and thickness of thecured portion was measured by a dial gauge of weak spring force to 0.1mm, to evaluate its curing speed. It was marked with ◯ when itsthickness was 1 mm or more, and × when it was less than 1 mm.

(2) Weather Resistance Test

The accelerated weather resistance test was conducted in accordance withJIS B-7753 under the following conditions:

-   Analyzer: Sunshine Carbon Arc weatherometer-   Light irradiation/rainfall cycles: Irradiation for 120-   minutes/rainfall for 18 minutes-   Black panel temperature: 63±2° C.-   Tank inside temperature: 40±2° C.-   Total light irradiation time: 250 hours

The tested test piece was visually observed, and marked with ◯ when nodeterioration (cracks or molten portion) was observed, and × when thedeterioration was observed.

TABLE V1 COMPARATIVE EXAMPLE EXAMPLE V1 V1 Silyl-containing ethylene/100 100 α-olefin/non-conjugated polyethylene copolymer rubber (A-1)Curing catalyst Curing catalyst (H8) 3 — Tin dioctylate — 3 Calciumcarbonate 120 120 Process oil 90 90 Titanium dioxide 30 30 Sodiumhydrogen sulfate 5 5 Tack-free (min) 16 >700 Curability ∘ x Resistanceto weather ∘ ∘

TABLE V2 REFERENCE EXAMPLE V 1 2 3 4 5 6 Saturated hydrocarbon-based D-1100 — — 100 — — Polymer D-2 — 100 — — 100 — D-3 — — 100 — — 100 Curingcatalyst Curing catalyst (H8) 3 3 3 — — — Tin dioctylate — — — 3 3 3Calcium carbonate 120 120 120 120 120 120 Process oil 90 90 90 90 90 90Titanium dioxide 30 30 30 30 30 30 Sodium hydrogen sulfate 5 5 5 5 5 5Tack-free (min) 25 30 30 >700 >700 >700 Curability X X X X X XResistance to weather ◯ ◯ ◯ ◯ ◯ ◯

Examples W Series

The composition, the iodine value, the intrinsic viscosity [η] and themolecular weight distribution (Mw/Mn) of the copolymer rubber used ineach of EXAMPLES and COMPARATIVE EXAMPLES were determined by the methodsdescribed earlier.

Curing speed and weather resistance of the compositions prepared inEXAMPLES, and COMPARATIVE and REFERENCE EXAMPLES were determined by thefollowing methods.

(1) Curing Speed Test

The curable composition was cured at 23° C. and 50% RH in a mold (80 by80 by 12. 5 mm in size), wherein hardness was followed by a JIS-Ahardness meter after surface tackiness disappeared, to record the timerequired for hardness to reach 20.

(2) Weather Resistance Test

-   Accelerated weather resistance test: Conducted in accordance with    JIS B-7753.-   Analyzer: Sunshine Carbon Arc weatherometer-   Light irradiation/rainfall cycles: Irradiation for 120-   minutes/rainfall for 18 minutes-   Black panel temperature: 63±2° C.-   Tank inside temperature: 40±2° C.-   Total light irradiation time: 500 hours

Production Example W1

[Production of Silyl-containing ethylene/propylene/5-vinyl-2-norborneneRandom Copolymer Rubber (A-1)]

The three-component copolymerization was effected continuously in astainless steel polymerization reactor having an essential capacity of100 L, equipped with agitator blades (agitating rotation speed: 250rpm), wherein hexane, ethylene, propylene and 5-vinyl-2-norbornene werecontinuously supplied at 60 L, 2.5 kg, 4.0 kg and 380 g per hour,respectively, from the reactor side into the liquid phase, and hydrogen,VO(OEt)₂Cl and Al(Et)_(1.5)Cl_(1.5) as the catalysts at 700 L, 45 mmolsand 315 mmols per hour, respectively, also continuously.

The copolymerization effected under the above conditions produced theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A₀-1)in a form of uniform solution.

A small quantity of methanol was added to the polymer solution,continuously withdrawn from the reactor bottom, to terminate thepolymerization. The polymer was separated from the solvent bysteam-stripping the solution, and dried at 55° C. for 48 hours under avacuum.

The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber(A₀-1) thus produced contained ethylene at 68% by mol, and had an iodinevalue of 10 (g/100 g), intrinsic viscosity [η], as measured in decalinkept at 135° C., of 0.2 dl/g, and Mw/Mn of 15.

Two % toluene solution (0.3 g) of chloroplatinic acid and 1.5 g ofmethyldimethoxysilane were added to 100 g of theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A₀-1),and they were allowed to react with each other at 120° C. for 2 hours.The excess methyldimethoxysilane and the solvent (toluene) weredistilled off from the effluent. This produced 101.5 g of theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A-1)containing dimethoxymethylsilyl group (—Si(CH₃)(OCH₃)₂).

Production Example W2

A 2 L pressure-resistant glass reactor was charged, after it wasequipped with a 3-way cock and purged with nitrogen, with 138 mL ofethyl cyclohexane (dried by molecular sieves 3A at least for a night),1012 mL of toluene (also dried by molecular sieves 3A at least for anight) and 8.14 g (35.2 mmols) of p-DCC represented by the followingformula by a syringe.

Next, a pressure-resistant glass-made liquefied gas collecting tubeequipped with a needle valve and containing 254 mL (2.99 mols) of anisobutylene monomer was connected to one side of the 3-way cock. Thenthe reactor for polymerization was immersed in a dry ice/ethanol bathkept at −70° C. to cool the solution, and evacuated to a vacuum using avacuum pump. It was then charged with the isobutylene monomer from theliquefied gas collecting tube by opening the needle valve, and returnedback to the normal pressure with a nitrogen gas introduced from anotherside of the 3-way cock. The reactor was charged with 0.387 g (4.15mmols) of 2-methyl pyridine and then with 4.90 mL (44.7 mmols) oftitanium tetrachloride, to initiate the polymerization. After a lapse of70 minutes, 9.65 g (13.4 mmols) of allyl trimethylsilane was added tothe reactor to introduce the allyl group at the polymer terminal. Aftera lapse of 120 minutes for the reaction, the reaction solution waswashed 4 times each with 200 mL of water, and the solvent was distilledoff to obtain the isobutylene-based polymer with the allyl group at theterminal.

Next, 200 g of the isobutylene-based polymer with the allyl group at theterminal thus obtained was mixed with 60 g of a paraffin-based processoil (Idemitsu Kosan, Diana Process Oil PS-32™) as the hydrocarbon-basedplastcizer, and the mixture was heated to around 75° C., to which 1.5[eq/vinyl group] of methyl dimethoxysilane and 5×10⁻⁵ [eq/vinyl group]of a platinum/vinyl siloxane complex were added, for thehydrosilylation. The reaction was followed by FT-IR. The olefinabsorption at 1640 cm⁻¹ disappeared in around 20 hours.

This produced the mixture of the isobutylene polymer (represented by thefollowing formula) having the reactive silicon group at both terminalsand PS-32 as the plasticizer (10/3 by weight).

The polymer yield was estimated from the quantity produced. It was alsoanalyzed for Mn and Mw/Mn by GPC, and the terminal structure bycomparing the intensities of the 300 MHz ¹H-NMR-analyzed resonancesignals of proton relevant to each structure (proton derived from theinitiator: 6.5 to 7.5 ppm, methyl proton bonded to the silicon atom,derived from the polymer terminal: 0.0 to 0.1 ppm, and methoxy proton:3.4 to 3.5 ppm) with each other. The ¹H-NMR analysis was conducted usinga Varian Gemini 300 (300 MHz for ¹H) in CDCl₃.

The FT-IR analysis was conducted by an IR analyzer (Shimadzu IR-408),and GPC analysis was conducted with a Waters LC Module 1 as the liquidsending system and Shodex K-804 as the column. The molecular weight wasthe one relative to the polystyrene standard. The polymer thus preparedhad an Mn of 5,780, Mw/Mn of 1.28 and Fn (silyl) of 1.93, wherein thenumber-average molecular weight was as polystyrene, and the number ofthe terminal functional silyl group was that per 1 mol of isobutylenepolymer.

Example W1

The silyl-containing ethylene/propylene/5-vinyl-2-norbornene randomcopolymer rubber (A-1), 130 parts, produced in PRODUCTION EXAMPLE W1,and a paraffin-based process oil (Idemitsu Kosan, Diana Process OilPS-₃₂™), in which the silyl-containingethylene/propylene/5-vinyl-2-norbornene random copolymer rubber as thecomponent (A-1) accounted for 100 parts, was incorporated with 5 partsof tetra-n-butyl titanate (Wako-Junyaku) as the titanates of thecomponent (Y), 2 parts of dibutyl tin bisacetylacetonate (NITTO KASEI,Neostann U-220™) as the silanol condensing catalyst and 1 part of H₂O,all parts by weight, to prepare the curable rubber composition.

The above composition was spread over a float glass substrate washedwith methylethylketone (Wako-Junyaku), which was not coated with aprimer, to a thickness of 5 mm, and cured in an oven. The curedcomposition was peeling-tested, in which it was manually released whilethe adhesive surface being cut by a cutter knife. The compositioncontaining 5 parts by weight of the titanate was well adhesive to thefloat glass substrate, showing the cohesion fracture. The curing speedand weather resistance tests were also conducted according to themethods described earlier. It took 18 hours until its hardness reached20 in the curing speed test, and showed no cracks in the weatherresistance test.

Comparative Example W1

The composition was prepared in the same manner as in EXAMPLE W1, exceptthat addition of the titanates as the component (Y) was omitted, andtested in the same manner. It was insufficient in adhesion to the floatglass substrate, showing the adhesion fracture. Moreover, it took 72hours or more until its hardness reached 20 in the curing speed test,and showed a number of cracks visible to the naked eye in the weatherresistance test.

Reference Example W1

The composition was prepared in the same manner as in COMPARATIVEEXAMPLE W1, except that the silyl-containingethylene/propylene/5-vinyl-2-norbornene random copolymer rubber preparedin PRODUCTION EXAMPLE W1 was replaced by the saturated hydrocarbon-basedpolymer containing the reactive silicon group prepared in PRODUCTIONEXAMPLE W2, and tested in the same manner. The manual peeling testresults indicated that the composition was insufficient in adhesion tothe float glass substrate, showing the adhesion fracture. Moreover, ittook 48 hours until its hardness reached 20 in the curing speed test,and showed cracks and molten portion visible to the naked eye, althoughslightly, in the weather resistance test.

Reference Example W2

The composition was prepared in the same manner as in EXAMPLE W1, exceptthat the silyl-containing ethylene/propylene/5-vinyl-2-norbornene randomcopolymer rubber prepared in PRODUCTION EXAMPLE W1 was replaced by thesaturated hydrocarbon-based polymer containing the reactive silicongroup prepared in PRODUCTION EXAMPLE W2, and tested in the same manner.The manual peeling test results indicated that the composition was goodin adhesion to the float glass substrate, showing the cohesion fracture.However, it took 36 hours until its hardness reached 20 in the curingspeed test, and showed cracks and molten portion, although slightly, inthe weather resistance test.

Examples X Series

The composition, the iodine value, the intrinsic viscosity [η] and themolecular weight distribution (Mw/Mn) of the copolymer rubber used ineach of EXAMPLES and COMPARATIVE EXAMPLES were determined by the methodsdescribed earlier.

Production Example X1

Production of Silyl-containing ethylene/propylene/5-vinyl-2-norborneneRandom Copolymer Rubber (A-1)

The three-component copolymerization was effected continuously in astainless steel polymerization reactor having an essential capacity of100 L, equipped with agitator blades (agitating rotation speed: 250rpm), wherein hexane, ethylene, propylene and 5-vinyl-2-norbornene werecontinuously supplied at 60 L, 3.0 kg, 9.0 kg and 550 g per hour,respectively, from the reactor side into the liquid phase, and hydrogen70 L, VOCl₃, Al(Et)₂Cl and Al(Et)_(1.5)Cl_(1.5) as the catalysts at 95mmols, 443 mmols and 127 mmols per hour, respectively, alsocontinuously.

The copolymerization effected under the above conditions produced theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber (A₀-1)in a form of uniform solution.

A small quantity of methanol was added to the polymer solution,continuously withdrawn from the reactor bottom, to terminate thepolymerization. The polymer was separated from the solvent bysteam-stripping the solution, and dried at 55° C. for 48 hours under avacuum.

The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber(A₀-1) thus produced contained ethylene at 68% by mol, and had an iodinevalue of 15 (g/100 g), intrinsic viscosity [η], as measured in decalinat 135° C., of 0.2 dl/g, and Mw/Mn of 15. The yield was 3.5 kg/h.

Two % toluene solution (0.3 part by weight) of chloroplatinic acid and1.5 parts by weight of methyldimethoxysilane were added to 100 parts byweight of the ethylene/propylene/5-vinyl-2-norbornene random copolymerrubber (A₀-1), and they were allowed to react with each other at 120° C.for 2 hours. The excess methyldimethoxysilane and the solvent (toluene)were distilled off from the effluent. This produced 101.5 parts byweight of the ethylene/propylene/5-vinyl-2-norbornene random copolymerrubber containing dimethoxymethylsilyl group (—SiH(OCH₃)₂).

Production Example X2

[Production of Saturated Hydrocarbon-Based Polymer (CA-1)]

A uniformly mixed solution of 560 mL of methylene chloride, 1,160 mL ofn-hexane, 940 mg of α-methylpyridine and 22 g of p-dicumyl chloride, alldried, was formed in a four-mouthed flask equipped with an agitator andnitrogen line and cooled to −70° C., in which 570 mL of isobutylenemonomer was charged under a vacuum through a molecular sieves tube.

A polymerization catalyst solution (comprising 14 mL of titaniumtetrachloride and 80 mL of methylene chloride) cooled beforehand wasadded all at once to the above reaction solution, kept at −70° C., withstirring to initiate the polymerization reaction. The reaction solutionwas heated to −54° C., and then cooled to −70° C. in about 17 minutes.About 20 minutes after the polymerization was initiated, 132 g of1,9-decadiene was added to the reaction solution, and continuouslystirred at −70° C. for 4 hours.

The yellowy turbid reaction solution thus produced was put in 3 L ofwarm water (around 45° C.) and stirred for around 2 hours. Then, theorganic layer was separated, and washed with pure water 3 times.

The resultant colorless, transparent organic layer was concentratedunder a vacuum, to obtain approximately 400 g of the isobutyleneoligomer with vinyl groups at both terminals.

Next, 400 g of the isobutylene oligomer with vinyl groups at bothterminals was dissolved in 200 mL of n-heptane. The resultant solutionwas heated to around 70° C., to which 1.5 [eq/vinyl group] of methyldimethoxysilane and 1×10⁻⁴[eq/vinyl group] of a platinum/vinyl siloxanecomplex were added, for the hydrosilylation. The reaction was followedby FT-IR. The olefin absorption at 1640 cm⁻¹ disappeared in around 4hours.

The reaction solution was concentrated under a vacuum, to obtain theisobutylene oligomer (represented by the following formula) having thereactive silicon group at both terminals.

Production Example X3

[Production of Saturated Hydrocarbon-Based Polymer (CA-2)]

The same procedure as used for PRODUCTION EXAMPLE X2 was repeated inPRODUCTION EXAMPLE X3, except that 1,9-decadiene was replaced by 24 g ofallylmethylsilane, to obtain the isobutylene oligomer (represented bythe following formula) of a partly different production intermediatestructure.

Production Example X4

[Production of Saturated Hydrocarbon-Based Polymer (CA-3)]

A uniformly mixed solution of 560 mL of methylene chloride, 1,160 mL ofn-hexane, 940 mg of α-methylpyridine and 22 g of p-dicumyl chloride, alldried, was formed in a four-mouthed flask equipped with an agitator andnitrogen line and cooled to −70° C., in which 570 mL of isobutylenemonomer was charged under a vacuum through a molecular sieves tube.

A polymerization catalyst solution (comprising 14 mL of titaniumtetrachloride and 80 mL of methylene chloride) cooled beforehand wasadded all at once to the above reaction solution, kept at −70° C., withstirring to initiate the polymerization reaction. The reaction solutionwas heated to −54° C., and then cooled to −70° C. in about 17 minutes.The reaction solution was continuously stirred for around 60 minutesafter the polymerization was initiated. The yellowy turbid reactionsolution thus produced was put in 3 L of warm water (around 45° C.) andstirred for around 2 hours. Then, the organic layer was separated, andwashed with pure water 3 times. The resultant colorless, transparentorganic layer was concentrated under a vacuum, to obtain approximately400 g of the isobutylene oligomer with chlorous groups at bothterminals.

Then, the isobutylene oligomer was continuously heated at 170° C. undera vacuum for 2 hours for the thermal dehydrochlorination reaction, toobtain the isobutylene oligomer with isopropenyl groups at bothterminals.

Next, 400 g of the isobutylene oligomer with isopropenyl groups at bothterminals was dissolved in 200 mL of n-heptane. The resultant solutionwas heated in a pressure vessel to around 100° C., to which 1.5[eq/vinyl group] of methyl dichlorosilane and 1×10⁻⁴ [eq/vinyl group] ofa platinum/vinyl siloxane complex were added, for the hydrosilylation.The reaction was followed by FT-IR. The olefin absorption at 1640 cm⁻¹disappeared in a round 10 hours. The reaction solution was cooled to60°, to which an excess quantity of methanol over methyl dichlorosilanewas added, and the mixture was stirred for around 4 hours, to completethe methoxylation. The reaction solution was concentrated under avacuum, to obtain the isobutylene oligomer having the structurerepresented by the following formula, with the reactive silicon group atboth terminals.

Synthesis Example 1

[Synthesis of Copolymer (B)]

A solution dissolving 5.7 g of butyl acrylate, 65.1 g of methylmethacrylate, 13.3 g of stearyl methacrylate, 5.6 g ofγ-methacryloxypropyltrimethoxysilane, 8.0 g ofγ-mercaptopropyltrimethoxysilane, 5.0 g of azobisisobutylonitrile and 22g of xylene was added dropwise to 20 g of xylene as the solvent heatedat 110° C. over 6 hours. They were allowed to react for polymerizationwith each other for 2 hours, to obtain the copolymer (B) containing thesolids at 70% and having a number-average molecular weight (Mn) of 2,100as polystyrene, determined by GPC.

Examples X1 to X5

The silyl-containing ethylene/propylene/5-vinyl-2-norbornene randomcopolymer rubber (A-1) prepared in PRODUCTION EXAMPLE X1 was blendedwith the copolymer (B) prepared in SYNTHESIS EXAMPLE 1 in a solid ratioof 60/40 by weight, and the mixture was evaporation-treated at 110° C.under a vacuum by an evaporator, to obtain the transparent, viscousliquid containing the solids at 99% or more.

The blended, evaporation-treated polymer, 100 g, was thoroughly kneadedwith 100 g of limestone powder, 50 g of colloidal calcium carbonate, 5 gof glass balloons (average particle size: 70 μm), 100 g of diisononylphthalate, 5 g of silicic anhydride, 2 g of a hindered phenol-basedaging inhibitor, 10 g of calcium oxide, 2 g of an aluminum chelate-basedcuring catalyst, 1 g of an aminosilane compound and a silicone-basedreactive diluent (Shin-etsu Silicone, AFP-1) by a planetary mixer, toobtain the sample (A-1) for EXAMPLES X1 to X5.

Reference Examples X1 to X9

The blended, evaporation-treated polymers were prepared for REFERENCEEXAMPLES X1 to X9 in the same manner as in EXAMPLES X1 to X5, exceptthat the silyl-containing

-   -   ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber        (A-1) prepared in PRODUCTION EXAMPLE X1 was replaced by the        saturated hydrocarbon-based polymers (CA-1) to (CA-3) prepared        in PRODUCTION EXAMPLES X2 to X4, respectively, and the samples        (CA-1) to (CA-3) were prepared for COMPARATIVE EXAMPLES X1 to X3        in the same manner as in EXAMPLES X1 to X5.

Comparative Examples X1 to X3

A vinyl chloride resin, 100 g, was thoroughly kneaded with 100 g oflimestone powder, 50 g of colloidal calcium carbonate, 5 g of glassballoons (average particle size: 70 μm), 100 g of diisononyl phthalate,3 g of lead-based dehydrochlorination inhibitor and 5 g of urethaneprepolymer by a planetary mixer, to obtain the sample (CA-4) forCOMPARATIVE EXAMPLES X1 to X3.

Each of these samples was spread over a cation-electro deposited steelplate to a thickness given in Table X1 under varying conditions alsogiven in Table X1, and cured to investigate its resistance to chipping,sprayed saline water and vibration. Resistance to weather and curingspeed of the coating film were evaluated by the following methods. Theresults are given in Table X1.

The test methods are described below.

(Resistance to Chipping)

Three types of nuts (Nut M-4) were dropped onto the sample slanted at45° from a height of 2 m until the base was exposed, and the chippingresistance was evaluated by the total weight of the nuts.

(Resistance to Sprayed Saline Water)

The sample coated on the cation-electrodeposited steel plate as the filmof a given thickness was cross-cut at the center to the base metal, andput in a tank sprayed with saline water for 200 hours. The resistance tosprayed saline water was evaluated by the maximum width of exfoliation,when a cellophane tape put on the cut surface was torn off.

(Resistance to Vibration)

The resistance to vibration was evaluated by the vibration insulationcoefficient (d), defined by the formula d=(f₂-f₁)/f₀ in accordance withthe vibration insulation test method for automobile underbody coatingmaterials (JASO7006), wherein f₀ is the resonance frequency at thesecondary resonance point, and f₂ and f₁ are frequencies at the sectionswhere sound intensity is decreased by 3 dB, the frequencies beingmeasured at 25° C.

(Curing Speed Test)

Tackiness-free Time at Medium Temperature

A cation-electrodeposited steel plate coated with the composition to athickness of 10 mm was kept at 60° C. in a drier. Tackiness of thecoating composition was measured at given time intervals by fingering.Tackiness-free time is defined as the time at which the composition isno longer transferred to the fingertip.

(Weather Resistance Test)

The weather resistance was evaluated by the accelerated weatherresistance test conducted in accordance with JIS B-7753 under thefollowing conditions:

-   Analyzer: Sunshine Carbon Arc weatherometer-   Light irradiation/rainfall cycles: Irradiation for 120    minutes/rainfall for 18 minutes-   Black panel temperature: 63±2° C.-   Tank inside temperature: 40±2° C.-   Total light irradiation time: 250 hours

The tested test piece was visually observed, to evaluate its resistanceto weather according to the following four grades:

-   ⊚: No cracks or molten portion observed entirely-   ◯: Cracks or molten portion observed very slightly-   Δ: Cracks or molten portion observed to some extent-   ×: Cracks or molten portion observed massively

TABLE X1 COMPARATIVE EXAMPLE X REFERENCE EXAMPLE X EXAMPLE X 1 2 3 4 5 12 3 4 5 6 7 8 9 1 2 3 A-1 CA-1 CA-2 CA-3 CA-4 Curing condition 140° C. ×30 min ◯ ◯ — — — ◯ ◯ — ◯ ◯ — ◯ ◯ — ◯ ◯ — 120° C. × 20 min — — ◯ — — — —◯ — — ◯ — — ◯ — — ◯ 120° C. × 10 min — — — ◯ — — — — — — — — — — — — —100° C. × 20 min — — — — ◯ — — — — — — — — — — — — Thickness of coatingfilm 1.5 mm ◯ — — — — ◯ — — ◯ — — ◯ — — ◯ — — 0.5 mm — ◯ ◯ ◯ ◯ — ◯ ◯ — ◯◯ — ◯ ◯ — ◯ ◯ Resistance to chipping 135 98 92 92 81 103 79 74 102 80 79101 73 77 68 41 9 Resistance to vibration 55 16 15 14 14 45 10 12 42 1112 42 11 13 8 5 4 (× 10³) Resistance to sprayed saline ≦1 ≦1 ≦1 ≦1 ≦1 ≦1≦1 1.2 ≦1 ≦1 1.3 ≦1 ≦1 1.3 ≦1 1.8 3.6 water (mm) Tack-free time (min) 3030 30 30 30 60 60 60 80 80 80 100 100 100 90 90 90 Resistance to weather⊚ ⊚ ⊚ ⊚ ⊚ Δ Δ Δ Δ Δ Δ Δ Δ Δ X X X

As shown in Table X1, the coating materials of the present invention forautomobiles exhibit excellent resistance to chipping, vibration, sprayedsaline water and weather, and also very high curing speed, even whencured at low temperature and for a short time, and also when it is thin.

Examples Y Series Production Example Y1

[Production of Silyl-containing ethylene/propylene/5-vinyl-2-norborneneRandom Copolymer Rubber]

The three-component copolymerization was effected continuously in astainless steel polymerization reactor having an essential capacity of100 L, equipped with agitator blades (agitating rotation speed: 250rpm), wherein hexane, ethylene, propylene and 5-vinyl-2-norbornene werecontinuously supplied at 60 L, 2.5 kg, 4.0 kg and 380 g per hour,respectively, from the reactor side into the liquid phase, and hydrogen,VO(OC₂H₅)₂Cl and Al(Et)_(1.5)Cl_(1.5) as the catalysts at 700 L, 45mmols and 315 mmols per hour, respectively, also continuously.

The copolymerization effected under the above conditions produced theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber in aform of uniform solution.

A small quantity of methanol was added to the polymer solution,continuously withdrawn from the reactor bottom, to terminate thepolymerization. The polymer was separated from the solvent bysteam-stripping the solution, and dried at 55° C. for 48 hours under avacuum.

The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber thusproduced contained ethylene at 68% bymol, and had an iodine value of 10,intrinsic viscosity [η] of 0.2 dl/g, and Mw/Mn of 15.

Two % toluene solution (0.3 g) of chloroplatinic acid and 1.5 g ofmethyldimethoxysilane were added to 100 g of theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber, andthey were allowed to react with each other at 120° C. for 2 hours. Theexcess methyldimethoxysilane and the solvent were distilled off from theeffluent. This produced 101.5 g of theethylene/propylene/5-vinyl-2-norbornene random copolymer rubbercontaining dimethoxymethylsilyl group.

Example Y1

The silyl-containing copolymer rubber prepared in PRODUCTION EXAMPLE Y1was incorporated with a paraffin-based process oil (Idemitsu Kosan,Diana Process Oil PS-32™), limestone powder (Maruo Calcium, SnowliteSS™) and salt cake (Na₂SO₄.10H₂O), and the mixture was well kneaded by a3-paint roll unit, to produce the major ingredient for the sealant. Therespective amounts as the part by weight are given in Table Y1. Dibutyltin bisacetylacetonate (NITTO KASEI, U-220™) was used as the curingcatalyst.

The major ingredient and curing catalyst as the component of the testsample were well kneaded, formed into an around 1.5 mm thick sheet andcured in an oven under the conditions of 23° C. and 50% RH for 7 daysand then 50° C. and 70% RH for another 7 days. The composition is givenin Table Y1.

The cured sheet sample was tested in accordance with JIS Z-0208 (themoisture-permeability test for moisture-proof packing materials) underthe temperature/humidity conditions B (40° C. and 90% RH).

The sample was evaluated by moisture permeability according to thefollowing three grades:

-   ◯: Permeability: 1 to 25 g/m²·24 hr-   Δ: Permeability: 25 to 50 g/m²·24 hr-   ×: Permeability: 50 g/m²·24 hr or more    The result is given in Table Y1.

Reference Example Y1

The sample was prepared and tested in the same manner as in EXAMPLE Y1,except that the silyl-containing copolymer rubber prepared in PRODUCTIONEXAMPLE Y1 was replaced by the isobutene polymer with a group containingreactive silicon at both terminals, prepared by the method disclosed byJapanese Patent Laid-open Publication No. 209539/1999 (paragraphs 0044to 0053). The moisture permeability result is given in Table Y1, whereinthe isobutene polymer with a group containing reactive silicon is listedin the column of the component (A).

TABLE Y1 REFERENCE EXAMPLE EXAMPLE Y1 Y1 Compositions (Major ingredient)Component (A2) Silyl-containing copolymer 100 — rubber, prepared inPRODUCTION EXAMPLE 1 Isobutene polymer containing — 100 reactive siliconOther additives Process oil (PS-32) 100 100 Limestone powder (SnowlightSS) 460 460 Na₂SO₄.10H₂O 2 2 Component (H) Curing agent (U-220) 4 4Characteristics of cured product Moisture permeability (g/m² · 24 hr) 00 Thickness (mm) 1.637 1.868

Examples Y2 to Y5

The major ingredient was prepared for each of EXAMPLES Y2 to Y5, wherethe silyl-containing copolymer rubber prepared in PRODUCTION EXAMPLE Y1was well kneaded by a 3-paint roll unit together with the additives:aging inhibitors (Ciba-Geigy Japan, Irganox 1010; Sumitomo Chemical,Sumisorb 400™, and Sankyo, Sanol LS-765™); light stabilizers (SanshinKagaku Kogyo, Sandant NBC™; and ACC, CYASORB UV-1084™); light-curableresin (TOAGOSEI, AronixM-400™); thixotropy imparting agent (KusumotoKasei, Disparlon #305™); silane coupling agents (Nippon Unicar, A-1310and A-187™). Each compositions is given in Table Y2.

The curing agent was prepared by the following procedure: a mixturecomprising a curing catalyst (Sankyo Organic Chemicals, Ltd., SCAT-27™)and other components was manually kneaded in a disposal cup and stirred3 times at 10,000 rpm each for 10 minutes by a homogenizer (Nihon SeikiSesakusho Co., Ltd., Excel Auto Homogenizer). Each composition is givenin Table Y2.

The test piece was prepared in accordance with JIS A-5758/1992specifying the method of preparing the test piece for tensile adhesiontest; the composition comprising the major ingredient and curing agent(composition is given in Table Y2) was put in the H-shape frame of glassor aluminum substrate after it was sufficiently kneaded, and cured in anoven under the conditions of 23° C. and 50% RH for 7 days and 50° C. and70% RH for another 7 days.

Three types of materials were used to prepare substrates for the H-typetensile test; float glass (Koen-sha, designated by Japan SealantIndustry Association, 3 by 5 by 0.5 cm in size) in accordance with JISA-5758/1992, pure aluminum (Taiyu Kizai, A1100P, 5 by 5 by 0.2 cm insize) in accordance with JIS H-4000, and heat ray reflective glass(KLS™, 5 by 5 by 0.6 cm in size) coated with thermally fused TiOx.

Each of these H-shapes was washed with methylethylketone (Wako-Junyaku,special grade) and wiped with clean cotton cloth, before it was filledwith the composition.

The H-shape test piece thus prepared was tested by the method of testingtensile adhesion in accordance with JIS A-5758/1992, wherein it wasstretched at a tensile speed of 50 mm/minute in a constant-temperaturechamber kept at 23° C. and 65±5%. The cohesion fracture CF)/thin-coatfracture (TCF)/adhesion fracture (AF) ratio shown in Table Y3 wasdetermined by visual observation of the cross-sections of thetensile-tested pieces.

As shown in Table Y3, all of the compositions prepared in EXAMPLES Y2 toY5 exhibit good adhesion to the substrate.

Reference Examples Y2 to Y5

The composition was prepared for each of REFERENCE EXAMPLES Y2 to Y5 andtested in the same manner as in EXAMPLES Y2 to Y5, except that thesilyl-containing copolymer rubber prepared in PRODUCTION EXAMPLE Y1 wasreplaced by the isobutene polymer prepared in REFERENCE EXAMPLE Y1 tohave a group containing reactive silicon at both terminals. The testresults are given in Table Y4.

TABLE Y2 EXAMPLES Y2 Y3 Y4 Y5 [Major ingredients] Polymer prepared in100 100 100 100 PRODUCTION EXAMPLE Y1 PS32 112.5 135 157 180 EDS-D10A62.5 75 87.5 100 PO320B10 22.5 270 315 360 Talc LMR 12.5 150 175 200Sandant NBC 3 3 3 3 Aronix M400 3 3 3 3 Disparlon #306 5 5 5 5 Sumisorp400 1 1 1 1 Sanol LS786 1 1 1 1 Irganox 1010 1 1 1 1 A-187 2 2 2 2 A13104 4 4 4 [Curing agents] SCAT-27 4 4 4 4 PS32 12.5 15 17.5 2.0 CB#30 2.52.5 2.5 2.5 Na₂SO₄.10H₂O 4 4 4 4 Snowlite SS 25 30 35 40 Polymer content(%) 14.4 12.4 10.9 9.7

TABLE Y3 50% Tensile Max. tensile Elongation stress stress at Fracturedconditions M50 Tmax the max. load (%) No. Substrates (kgf/cm²) (kgf/cm²)Emax (%) CF TCF AF EXAMPLE Y2 Float glass 1 4.46 6.17 87 100 0 0 2 4.666.20 86 100 0 0 average 4.64 6.19 87 100 0 0 Pure aluminum 1 4.39 6.2191 99 1 0 2 4.37 6.10 87 100 0 0 average 4.38 6.16 98 100 0 0 KLS 1 4.676.22 88 99 1 0 2 4.69 6.25 93 100 0 0 average 4.68 6.24 91 100 0 0EXAMPLE Y3 Float glass 1 4.69 6.26 86 98 2 0 2 4.71 6.27 84 98 2 0average 4.70 6.27 85 98 2 0 Pure aluminum 1 4.37 6.18 87 99 1 0 2 4.356.12 82 100 0 0 average 4.36 6.15 85 100 0 0 KLS 1 4.80 6.32 80 97 3 0 24.83 6.36 79 97 3 0 average 4.82 6.34 80 97 3 0 EXAMPLE Y4 Float glass 14.66 6.11 72 98 2 0 2 4.69 6.02 74 100 0 0 average 4.68 6.07 73 99 1 0Pure aluminum 1 4.36 6.11 79 92 7 0 2 4.33 6.08 77 97 3 0 average 4.356.05 78 95 5 0 KLS 1 4.67 6.13 75 99 1 0 2 4.70 6.11 72 99 1 0 average4.69 6.12 74 99 1 0 EXAMPLE Y5 Float glass 1 4.33 6.27 70 98 2 0 2 4.306.23 73 99 1 0 average 4.32 6.25 72 99 1 0 Pure aluminum 1 3.76 5.89 7399 2 0 2 3.72 5.91 77 98 2 0 average 3.74 5.90 75 98 2 0 KLS 1 4.32 6.1878 100 0 0 2 4.37 6.11 71 100 0 0 average 4.35 6.15 75 100 0 0

TABLE Y4 50% Tensile Max. tensile Elongation stress stress at Fracturedconditions M50 Tmax the max. load (%) No. Substrates (kgf/cm²) (kgf/cm²)Emax (%) CF TCF AF REFERENCE Float glass 1 4.67 6.98 98 100 0 0 EXAMPLEY2 2 4.76 6.87 91 100 0 0 average 4.72 6.93 95 100 0 0 Pure aluminum 14.43 6.51 91 100 0 0 2 4.38 7.01 106 99 1 0 average 4.41 6.76 99 100 1 0KLS 1 4.79 7.25 99 98 2 0 2 4.66 7.43 105 100 0 0 average 4.73 7.34 10299 1 0 REFERENCE Float glass 1 4.74 6.70 89 95 5 0 EXAMPLE Y3 2 4.797.10 93 85 15 0 average 4.77 6.90 91 90 10 0 Pure aluminum 1 4.38 6.8194 100 0 0 2 4.43 6.53 85 95 6 0 average 4.41 6.67 90 98 3 0 KLS 1 4.926.58 81 90 10 0 2 5.03 6.86 83 90 10 0 average 4.98 6.72 82 90 10 0REFERENCE Float glass 1 4.75 6.32 77 98 2 0 EXAMPLE Y4 2 4.79 6.43 77100 0 0 average 4.77 6.38 77 95 1 0 Pure aluminum 1 4.38 6.34 86 85 16 02 4.53 5.94 75 100 0 0 average 4.46 6.14 81 100 8 0 KLS 1 4.68 6.29 8199 1 0 2 4.83 6.17 74 90 10 0 average 4.76 6.23 78 100 6 0 REFERENCEFloat glass 1 4.28 6.00 79 95 5 0 EXAMPLE Y5 2 4.36 5.98 76 100 0 0average 4.32 5.99 78 98 3 0 Pure aluminum 1 3.92 5.38 79 95 5 0 2 3.996.13 87 98 2 0 average 3.96 5.76 83 97 4 0 KLS 1 4.37 6.35 85 100 0 0 24.83 5.86 70 100 0 0 average 4.60 6.11 78 100 0 0

The curing speed and weather resistance tests were conducted for thecompositions prepared in EXAMPLES Y1 to Y5 and REFERENCE EXAMPLES Y1 toY5. The results are given in Table Y5.

The curing speed and resistance to weather were measured for thecompositions prepared in EXAMPLES Y1 to Y5 and REFERENCE EXAMPLES Y1 toY5 by the following methods.

1) Curing Speed

Each of the compositions comprising the major ingredient and catalystwas measured for curing speed (film expandability) at room temperatureby the method in which the composition was cured at 23° C. and 50% RHfor 24 hours in a mold (20 by 80 by 5 mm in size), and then releasedfrom the mold. Thickness of the cured portion was measured by a dialgauge of weak spring force to 0.1 mm.

<Evaluation Standards for Curing Speed>

-   ×: The cured portion was less than 0.5 mm thick-   Δ: The cured portion was 0.5 mm thick or more but less than 1 mm-   ◯: The cured portion was 1 mm thick or more.    2) Weather Resistance Test

The accelerated weather resistance test was conducted in accordance withJIS B-7753 under the following conditions:

-   Analyzer: Sunshine Carbon Arc weatherometer-   Light irradiation/rainfall cycles: Irradiation for 120    minutes/rainfall for 18 minutes-   Black panel temperature: 63±2° C.-   Tank inside temperature: 40±2° C.-   Total light irradiation time: 500 hours

The tested test piece was visually observed, to evaluate its resistanceto weather according to the following three grades:

TABLE Y5 Resistance to weather Curing speed EXAMPLE Y1 ∘ ∘ EXAMPLE Y2 ∘∘ EXAMPLE Y3 ∘ ∘ EXAMPLE Y4 ∘ ∘ EXAMPLE Y5 ∘ ∘ REFERENCE EXAMPLE Y1 Δ xREFERENCE EXAMPLE Y2 Δ x REFERENCE EXAMPLE Y3 Δ x REFERENCE EXAMPLE Y4 Δx REFERENCE EXAMPLE Y5 Δ x ∘: No cracks or molten portion observed Δ:Cracks or molten portion observed slightly x: Cracks or molten portionobserved

Examples Z Series Production Example Z1

[Production of Silyl-containing ethylene/propylene/5-vinyl-2-norborneneRandom Copolymer Rubber]

The three-component copolymerization was effected continuously in astainless steel polymerization reactor having an essential capacity of100 L, equipped with agitator blades (agitating rotation speed: 250rpm), wherein hexane, ethylene, propylene and 5-vinyl-2-norbornene werecontinuously supplied at 60 L, 2.5 kg, 4.0 kg and 380 g per hour,respectively, from the reactor side into the liquid phase, and hydrogen,VO(OC₂H₅)₂Cl and Al(Et)_(1.5)Cl_(1.5) as the catalysts at 700 L, 45mmols and 315 mmols per hour, respectively, also continuously.

The copolymerization effected under the above conditions produced theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber in aform of uniform solution.

A small quantity of methanol was added to the polymer solution,continuously withdrawn from the reactor bottom, to terminate thepolymerization. The polymer was separated from the solvent bysteam-stripping the solution, and dried at 55° C. for 48 hours under avacuum.

The ethylene/propylene/5-vinyl-2-norbornene random copolymer rubber thusproduced contained ethylene at 68% by mol, and had an iodine value of10, intrinsic viscosity [η] of 0.2 dl/g, and Mw/Mn of 15.

Two % toluene solution (0.3 g) of chloroplatinic acid and 1.5 g ofmethyldimethoxysilane were added to 100 g of theethylene/propylene/5-vinyl-2-norbornene random copolymer rubber, andthey were allowed to react with each other at 120° C. for 2 hours. Theexcess methyldimethoxysilane and the solvent were distilled off from theeffluent. This produced 101.5 g of the copolymer rubber containingdimethoxymethylsilyl group.

Examples Z1 to Z3, and Comparative Example Z1

The polymer prepared in PRODUCTION EXAMPLE Z1, 100 parts wasincorporated with 30 parts of a paraffin-based process oil (IdemitsuKosan, Diana Process Oil PS-32™), 130 parts of a butyl-based hot melt(Yokohama Rubber, Hamatite HOTMELT M-120), 6 parts of salt cake(reagent, Na₂SO₄.10H₂O), 3 parts of tin octylate (NITTO KASEI, NeostannU-28™) and 0.75 part of lauryl amine (Wako Jun-yaku), all parts byweight. The mixture was well kneaded by a 3-paint roll unit, to producethe test sample for EXAMPLE Z1.

The compositions were prepared for EXAMPLES Z2 and Z3 in the same manneras in EXAMPLE Z1, except that contents of the butyl-based hot melt werechanged to 303.3 and 1169 parts by weight, respectively, to prepare thetest samples. The composition was also prepared for COMPARATIVE EXAMPLEZ1 in the same manner as in EXAMPLE Z1, except that the polymer wasincorporated only with the hot melt to prepare the test sample. Thesesamples were used for the tensile test.

The test sample was prepared in accordance with JIS A-6850/1976 whichspecifies the method of sample preparation for testing tensile adhesionstrength of adhesives. Each composition was spread over and pressed toan aluminum plate (Taiyu Kizai, A-1050P, 2.5 by 10 by 0.3 mm in size,specified by JIS H-4000) as the substrate, which was washed withmethylethylketone (Wako Jun-yaku) and wiped with clean cotton clothbeforehand. Each composition was cured as the sealing material at 50° C.for 4 days in an oven.

The test sample prepared by the above method was stretched at 50mm/minute in a constant-temperature chamber kept at 23° C. and RH65±5%,in accordance with JIS A-6850 for the tensile adhesion testing method.The results are given in Table Z1.

Reference Examples Z1 to Z3

The isobutene polymer was prepared and tested in each of REFERENCEEXAMPLES Z1 to Z3 in the same manner as in corresponding EXAMPLE Z1, Z2or Z3, except that the silyl-containing copolymer rubber prepared inPRODUCTION EXAMPLE Z1 was replaced by the isobutene polymer with a groupcontaining reactive silicon at both terminals, prepared according to themethod disclosed by Japanese Patent Laid-open Publication No.209540/1999 (paragraphs 0041 to 0050). The results are given in TableZ1, together with the results of the curing speed and weather resistancetests.

The curing speed and resistance to weather were measured by thefollowing methods.

1) Curing Speed

Each of the compositions comprising the major ingredient and catalyst asdescribed above was measured for curing speed (film expandability) atroom temperature by the following method:

The composition was cured in a chamber kept at 23° C. and 50% RH for 24hours in a mold (20 by 80 by 5 mm in size), and then released from themold. Thickness of the cured portion was measured by a dial gauge ofweak spring force to 0.1 mm.

<Evaluation Standards for Curing Speed>

-   ×: The cured portion was less than 1 mm thick.-   ◯: The cured portion was 1 mm thick or more.    2) Weather Resistance Test

The accelerated weather resistance test was conducted in accordance withJIS B-7753 under the following conditions:

-   Analyzer: Sunshine Carbon Arc weatherometer-   Light irradiation/rainfall cycles: Irradiation for 120-   minutes/rainfall for 18 minutes-   Black panel temperature: 63±2° C.-   Tank inside temperature: 40±2° C.-   Total light irradiation time: 500 hours

The tested test piece was visually observed, to evaluate its resistanceto weather according to the following three grades:

TABLE Z1 Max.tensile stress Elongation at Tmax the max. load Resistanceto (kgf/cm²) Emax (%) Curing speed weather EXAMPLE Z1 1 2.1 90 ◯ ◯ 2 1.9100 average 2.0 95 EXAMPLE Z2 1 2.0 76 ◯ ◯ 2 1.8 84 average 1.9 80EXAMPLE Z3 1 1.8 55 — — 2 1.6 65 average 1.7 60 COMPARATIVE 1 1.2 45 X ΔEXAMPLE Z1 2 1.4 35 average 1.3 40 REFERENCE 1 2.1 32 X Δ EXAMPLE Z1 22.1 28 average 2.1 30 REFERENCE 1 1.5 12 X Δ EXAMPLE Z2 2 1.7 8 average1.6 10 REFERENCE 1 1.6 18 — — EXAMPLE Z3 2 1.6 22 average 1.6 20 ◯: Nocracks or molten portion observed Δ: Cracks or molten portion observedslightly X: Cracks or molten portion observed

Example Z4 and Reference Example Z4

The cured sheet of about 2 mm thickness was prepared using thecomposition produced in each of EXMPLE Z1 and REFERENCE EXAMPLE Z1. Thecured sheet was stamped out into the No. 3 dumbbell-shaped test piece inaccordance with JIS K-6301. The results of tensile test are shown inTable Z2 (EXAMPLE Z4) and Table Z3 (REFERENCE EXAMPLE Z4), respectively.The test piece was cured at 23° C. for 7 days and at 50° C. for another7 days, and then taken out for measurement of H-type mechanicalcharacteristics.

The test was conducted at a stretching speed of 200 mm/min in athermostat kept at 23, 50 and 70° C. according to the method of thetensile test specified by JIS K-6301.

TABLE Z2 50% Tensile stress 100% Tensile stress Max.tensile stressElongation at EXAMPLE M50 M100 Tmax the max. load Z4 (kgf/cm²) (kgf/cm²)(kgf/cm²) Emax (%) 23 1 1.1 1.6 10.0 560 (° C.) 2 0.9 1.5 10.5 480 3 1.01.7 9.5 520 Average 1.0 1.6 10.0 520 50 1 0.9 1.5 4.5 390 (° C.) 2 0.71.5 5.5 370 3 0.8 1.2 5.0 380 Average 0.8 1.4 5.0 380 70 1 0.8 1.5 4.1340 (° C.) 2 0.8 1.5 4.0 340 3 0.7 1.4 3.9 320 Average 0.8 1.5 4.0 330

TABLE Z3 REFERENCE 50% Tensile stress 100% Tensile stress Max.tensilestress Elongation at EXAMPLE M50 M100 Tmax the max. load Z4 (kgf/cm²)(kgf/cm²) (kgf/cm²) Emax (%) 23 1 1.0 1.7 9.2 410 (° C.) 2 1.1 1.7 11.0480 3 1.2 1.9 11.7 470 Average 1.1 1.8 10.6 450 50 1 0.9 1.5 4.4 310 (°C.) 2 0.8 1.5 5.1 320 3 1.0 1.7 5.8 330 Average 0.9 1.5 5.1 320 70 1 1.01.7 5.0 330 (° C.) 2 0.9 1.6 4.4 300 3 0.9 1.5 3.5 260 Average 0.9 1.64.3 300

1. A curable composition comprising a silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1)which has a structural unit derived from a norbomene compound,represented by the following general formula [I] or [II], as thenon-conjugated polyene with at least one specific vinyl group at theterminal, and containing a hydrolyzable silyl group, represented bygeneral formula [III], and

wherein, “n” is an integer of 0 to 10; R¹ is a hydrogen atom or an alkylgroup of 1 to 10 carbon atoms; and R² is a hydrogen atom or an alkylgroup of 1 to 5 carbon atoms,

wherein, R³ is a hydrogen atom or an alkyl group of 1 to 10 carbonatoms,

wherein, R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; Xis a hydrolyzable group selected from the group consisting of hydride,halogen, alkoxyl, acyloxy, ketoximate, amide, acid amide, aminoxy,mercapto, alkenyloxy, thioalkoxy and amino group; and “a” is an integerof 0 to 2, wherein the rubber (A1) is produced by hydrosilylation,whereby said ethylene/α-olefin/non-conjugated polyene random copolymerrubber is reacted with a silicon compound represented by the followinggeneral formula [IV] in the presence of a transition metal complexcatalyst:

where R and “a” are as defined above; and a compound (B), other than therubber (A1), having a hydroxyl group and/or a hydrolyzable group.
 2. Acurable, elastic composition comprising a silyl-containingethylene/α/non-conjugated polyene random copolymer rubber (A1) which hasa structural unit derived from a norbomene compound, represented by thefollowing general formula [I] or [II], as the non-conjugated polyenewith at least one specific vinyl group at the terminal, and containing ahydrolyzable silyl group, represented by the following general formula[III], and

wherein, “n” is an integer of 0 to 10; R¹ is a hydrogen atom or an alkylgroup of 1 to 10 carbon atoms; and R² is a hydrogen atom or an alkylgroup of 1 to 5 carbon atoms,

wherein, R³ is a hydrogen atom or an alkyl group of 1 to 10 carbonatoms,

wherein, R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; Xis a hydrolyzable group selected from the group consisting of hydride,halogen, alkoxyl, acyloxy, ketoximate, amide, acid amide, aminoxy,mercapto, alkenyloxy, thioalkoxy and amino group; and “a” is an integerof 0 to 2, wherein the rubber (A1) is produced by hydrosilylation,whereby said ethylene/α-olefin/non-conjugated polyene random copolymerrubber is reacted with a silicon compound represented by the followinggeneral formula [IV] in the presence of a transition metal complexcatalyst:

wherein R and “a” are as defined above; and a compound (B1) having asilanol group and/or a compound which can react with moisture to form acompound having a silanol group in the molecule.
 3. A curable rubbercomposition comprising a silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1)which has a structural unit derived from a norbomene compound,represented by the following general formula [I] or [II], as thenon-conjugated polyene with at least one specific vinyl group at theterminal, and containing a hydrolyzable silyl group, represented by thefollowing general formula [III],

wherein, “n” is an integer of 0 to 10; R¹ is a hydrogen atom or an alkylgroup of 1 to 10 carbon atoms; and R² is a hydrogen atom or an alkylgroup of 1 to 5 carbon atoms,

wherein, R³ is a hydrogen atom or an alkyl group of 1 to 10 carbonatoms,

wherein, R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; Xis a hydrolyzable group selected from the group consisting of hydride,halogen, alkoxyl, acyloxy, ketoximate, amide, acid amide, aminoxy,mercapto, alkenyloxy, thioalkoxy and amino group; and “a” is an integerof 0 to 2, wherein the rubber (A1) is produced by hydrosilylation,whereby said ethylene/α-olefin/non-conjugated polyene random copolymerrubber is reacted with a silicon compound represented by the followinggeneral formula [IV] in the presence of a transition metal complexcatalyst:

wherein R and “a” are as defined above; a tetravalent tin compound (C),and a silicon compound (B2) represented by the following general formula[V]:R⁴ _(a)Si(OR⁵)_(4-a)  [V] wherein, R⁴ and R⁵ are each a substituted orunsubstituted hydrocarbon group of 1 to 20 carbon atoms, and “a” is 0,1, 2, or
 3. 4. A curable composition comprising (a) a silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1)which has a structural unit derived from a norbomene compound,represented by the following general formula [I] or [II], as thenon-conjugated polyene with at least one specific vinyl group at theterminal, and containing a hydrolyzable silyl group, represented by thefollowing general formula [III],

wherein, “n” is an integer of 0 to 10; R¹ is a hydrogen atom or an alkylgroup of 1 to 10 carbon atoms; and R² is a hydrogen atom or an alkylgroup of 1 to 5 carbon atoms,

wherein, R³ is a hydrogen atom or an alkyl group of 1 to 10 carbonatoms,

wherein, R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; Xis a hydrolyzable group selected from the group consisting of hydride,halogen, mercapto, alkenyloxy, alkoxyl, acyloxy, ketoximate, amide, acidamide, aminoxy, thioalkoxy and amino group; and “a” is an integer of 0to 2, and (b) a silicon compound (B3) having at least one amino groupand at least one trialkylsiloxy group in the molecule.
 5. A curablecomposition comprising (a) a silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1)which has a structural unit derived from a norbomene compound,represented by the following general formula [I] or [II], as thenon-conjugated polyene with at least one specific vinyl group at theterminal, and containing a hydrolyzable silyl group, represented by thefollowing general formula [III],

wherein, “n” is an integer of 0 to 10; R¹ is a hydrogen atom or an alkylgroup of 1 to 10 carbon atoms; and R² is a hydrogen atom or an alkylgroup of 1 to 5 carbon atoms,

wherein, R³ is a hydrogen atom or an alkyl group of 1 to 10 carbonatoms,

wherein, R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; Xis a hydrolyzable group selected from the group consisting of hydride,halogen, mercapto, alkenyloxy, alkoxyl, acyloxy, ketoximate, amide, acidamide, aminoxy, thioalkoxy and amino group; and “a” is an integer of 0to 2, and (b) an organosilicon compound (B4) represented by thefollowing general formula [VI]:(R²(CH₃)₂SiO)_(n)R¹  [VI] wherein, R¹ is an alcohol residue or a weakacid residue, R² is a methyl or vinyl group, and “n” is a positiveinteger.
 6. A rubber composition curable at an ordinary temperature andcomprising a silyl-containing ethylene/α-olefin/non-conjugated polyenerandom copolymer rubber (A1) which has a structural unit derived from anorbornene compound, represented by the following general formula [I] or[II], as the non-conjugated polyene with at least one specific vinylgroup at the tenninal, and containing a hydrolyzable silyl group,represented by the following general formula [III],

wherein, “n” is an integer of 0 to 10; R¹ is a hydrogen atom or an alkylgroup of 1 to 10 carbon atoms; and R² is a hydrogen atom or an alkylgroup of 1 to 5 carbon atoms,

wherein, R³ is a hydrogen atom or an alkyl group of 1 to 10 carbonatoms,

wherein, R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; Xis a hydrolyzable group selected from the group consisting of hydride,halogen, alkoxyl, acyloxy, ketoximate, amide, acid amide, aminoxy,mercapto, alkenyloxy, thioalkoxy and amino group; and “a” is an integerof 0 to 2, and a silane compound (B5) represented by one of thefollowing general formulae [VII-1] to [VII-6]:

wherein, R⁴ is a monovalent hydrocarbon group of 1 to 10 carbon atoms,selected from the group consisting of alkyl, aralkyl and aryl; X is agroup selected from the group consisting of halogen, hydroxy, alkoxyl,acyloxy, aminoxy, phenoxy, thioalkoxy, amino, ketoximate, mercapto andalkenyloxy; R⁵ is an alkylene or arylene group of 8 to 200 carbon atoms;R⁶ is a monovalent alkyl group of 8 to 200 carbon atoms; and “n” is aninteger of 0 to
 2. 7. A curable rubber composition comprising, as theactive components, (A1) a silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber whichhas a structural unit derived from a norbomene compound, represented bythe following general formula [I] or [II], as the non-conjugated polyenewith at least one specific vinyl group at the terminal, and containing ahydrolyzable silyl group, represented by the following general formula[III],

wherein, “n” is an integer of 0 to 10; R¹ is a hydrogen atom or an alkylgroup of 1 to 10 carbon atoms; and R² is a hydrogen atom or an alkylgroup of 1 to 5 carbon atoms, the following general formula [I] or [II],as the non-conjugated polyene with at least one specific vinyl group atthe terminal, and containing a hydrolyzable silyl group, represented bythe following general formula [III],

wherein, “n” is an integer of 0 to 10; R¹ is a hydrogen atom or an alkylgroup of 1 to 10 carbon atoms; and R² is a hydrogen atom or an alkylgroup of 1 to 5 carbon atoms,

wherein, R³ is a hydrogen atom or an alkyl group of 1 to 10 carbonatoms,

wherein, R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; Xis a hydrolyzable group selected from the group consisting of hydride,halogen, mercapto, alkenyloxy, alkoxyl, acyloxy, ketoximate, amide, acidamide, aminoxy, thioalkoxy and amino

wherein, R³ is a hydrogen atom or an alkyl group of 1 to 10 carbonatoms,

wherein, R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; Xis a hydrolyzable group selected from the group consisting of hydride,halogen, alkoxyl, acyloxy, ketoximate, amide, acid amide, aminoxy,mercapto, alkenyloxy, thioalkoxy and amino group; and “a” is an integerof 0 to 2, (D) amines selected from the group consisting of aliphaticamines, alicyclic amines, modified cycloaliphatic polyamines andethanolamines, (B6) a silane coupling agent represented by the generalformula Y₃(Si)Z, wherein Y is an alkoxyl group; and Z is an alkyl groupcontaining a functional group selected from the group consisting ofamino group, which may be substituted with an aminoalkyl group or not,and mercapto group, and (E) a resin composed of a lacquer-based paint,an acrylic lacquer-based paint, an acrylic resin-based paint, athermosetting acrylic paint, an alkyd paint, a melamine paint, an epoxypaint or organopolysiloxane.
 8. A curable composition comprising, (a) asilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1) which has a structural unit derived from anorbomene compound, represented by group; and “a” is an integer of 0 to2, wherein the rubber (A1) is produced by hydrosilylation, whereby saidethylene/α-olefin/non-conjugated polyene random copolymer rubber isreacted with a silicon compound represented by the following generalformula [IV] in the presence of a transition metal complex catalyst:

wherein R and “a” are as defined above; and (b) a silane-based compound(B7) substituted with an amino group.
 9. A curable compositioncomprising, (A1) a silyl-containing ethylene/α-olefin/non-conjugatedpolyene random copolymer rubber which has a structural unit derived froma norbornene compound, represented by the following general formula [I]or [II], as the non-conjugated polyene with at least one specific vinylgroup at the terminal, and containing a hydrolyzable silyl group,represented by the following general formula [III],

wherein, “n” is an integer of 0 to 10; R¹ is a hydrogen atom or an alkylgroup of 1 to 10 carbon atoms; and R² is a hydrogen atom or an alkylgroup of 1 to 5 carbon atoms,

wherein, R³ is a hydrogen atom or an alkyl group of 1 to 10 carbonatoms,

wherein, R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; Xis a hydrolyzable group selected from the group consisting of hydride,halogen, mercapto, alkenyloxy, alkoxyl, acyloxy, ketoximate, amide, acidamide, aminoxy, thioalkoxy and amino group; and “a” is an integer of 0to 2, and (F) a filler, (G) a plasticizer, (H) a curing catalyst and(B8) an organocarboxylic acid compound.
 10. A curable rubber compositioncomprising, a silyl-containing ethylene/α-olefin/non-conjugated polyenerandom copolymer rubber (A1) which has a structural unit derived from anorbomene compound, represented by the following general formula [I] or[II], as the non-conjugated polyene with at least one specific vinylgroup at the terminal, and containing a hydrolyzable silyl group,represented by the following general formula [III],

wherein, “n” is an integer of 0 to 10; R¹ is a hydrogen atom or an alkylgroup of 1 to 10 carbon atoms; and R² is a hydrogen atom or an alkylgroup of 1 to 5 carbon atoms,

wherein, R³ is a hydrogen atom or an alkyl group of 1 to 10 carbonatoms,

wherein, R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; Xis a hydrolyzable group selected from the group consisting of hydride,halogen, alkoxyl, acyloxy, ketoximate, amide, acid amide, aminoxy,mercapto, alkenyloxy, thioalkoxy and amino group; and “a” is an integerof 0 to 2, wherein the rubber (A1) is produced by hydrosilylation,whereby said ethylene/α-olefin/non-conjugated polyene random copolymerrubber is reacted with a silicon compound represented by the followinggeneral formula [IV] in the presence of a transition metal complexcatalyst:

wherein R and “a” are as defined above; alcohols (B9) and/or ahydrolyzable ester (I) (except the hydrolyzable organosilicon compound(B10), and a hydrolyzable organosilicon compound (B10) other than therubber (A1).
 11. A two- or more multi-liquid type curable rubbercomposition composed of at least two liquids, comprising a majoringredient (I) containing a silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1)which has a structural unit derived from a norbomene compound,represented by the following general formula [I] or [II], as thenon-conjugated polyene with at least one specific vinyl group at theterminal, and containing a hydrolyzable silyl group, represented by thefollowing general formula [III],

wherein, “n” is an integer of 0 to 10; R¹ is a hydrogen atom or an alkylgroup of 1 to 10 carbon atoms; and R² is a hydrogen atom or an alkylgroup of 1 to 5 carbon atoms,

wherein, R³ is a hydrogen atom or an alkyl group of 1 to 10 carbonatoms,

wherein, R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; Xis a hydrolyzable group selected from the group consisting of hydride,halogen, alkoxyl, acyloxy, ketoximate, amide, acid amide, aminoxy,mercapto, alkenyloxy, thioalkoxy and amino group; and “a” is an integerof 0 to 2, wherein the rubber (A1) is produced by hydrosilylation,whereby said ethylene/α-olefin/non-conjugated polyene random copolymerrubber is reacted with a silicon compound represented by the followinggeneral formula [IV] in the presence of a transition metal complexcatalyst:

wherein R and “a” are as defined above; and a curing agent (II)containing asilanol condensing catalyst (J) and water or a hydrate of ametallic salt (B11).
 12. A curable rubber composition comprising asilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A2) containing a hydrolyzable silyl group, representedby the following general formula (1):

wherein, R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; Xis a hydrolyzable group selected from the group consisting of hydride,halogen, alkoxyl, acyloxy, ketoximate, amide, acid amide, aminoxy,thioalkoxy, amino, mercapto and alkenyloxy group; and “m” is an integerof 0 to 2, and an inorganic filler (L), wherein the rubber (A2) isproduced by hydrosilylation, whereby saidethylene/α-olefin/non-conjugated polyene random copolymer rubber isreacted with a silicon compound represented by the following generalformula (6) in the presence of a transition metal complex catalyst:

where R and “m” are as defined above.
 13. A rubber compositioncomprising a silyl-containing ethylene/α-olefin/non-conjugated polyenerandom copolymer rubber (A2) containing a hydrolyzable silyl group,represented by the following general formula (1):

wherein, R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; Xis a hydrolyzable group selected from the group consisting of hydride,halogen, alkoxyl, acyloxy, ketoximate, amide, acid amide, aminoxy,thioalkoxy, amino, mercapto and alkenyloxy group; and “m” is an integerof 0 to 2, and (K1) an organosilicon polymer.
 14. A rubber compositioncomprising (A2) a silyl-containing ethylene/α-olefin/non-conjugatedpolyene random copolymer rubber containing a hydrolyzable silyl group,represented by the following general formula (1):

wherein, R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; Xis a hydrolyzable group selected from the group consisting of hydride,halogen, alkoxyl, acyloxy, ketoximate, amide, acid amide, aminoxy,thioalkoxy, amino, mercapto and alkenyloxy group; and “m” is an integerof 0 to 2, (K2) organic rubber which is at least one rubber selectedfrom the group consisting of propylene glycol-based rubber containing ahydrolysable silyl group, polyisobutylene-based rubber containing ahydrolysable silyl group, natural rubber, polyisoprene, polybutadienepolychloroprene, acrylic rubber, acrylonitrile/butadiene copolymerrubber, ethylene/propylene copolymer rubber (EPM),ethylene/propylene/non-conjugated polyene copolymer rubber (EPDM), butylrubber, urethane rubber, silicone rubber, epichlorohydrin rubber,ethylene/vinyl acetate copolymer rubber, ethylene/acrylic copolymerrubber, fluorine rubber and chlorosulfonated polyethylene, and (M) acrosslinking agent for the organic rubber (K2).
 15. A rubber compositioncomprising (A2) a silyl-containing ethylene/α-olefin/non-conjugatedpolyene random copolymer rubber containing a hydrolyzable silyl group,represented by the following general formula (1):

wherein, R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; Xis a hydrolyzable group selected from the group consisting of hydride,halogen, alkoxyl, acyloxy, ketoximate, amide, acid amide, aminoxy,thioalkoxy, amino, mercapto and alkenyloxy group; and “m” is an integerof 0 to 2, (K3) an epoxy resin, (N) a silane coupling agent, (O) asilanol condensing catalyst, and (P) a curing agent for the epoxy resin.16. A rubber composition comprising (A2) a silyl-containingethylene/μ-olefin/non-conjugated polyene random copolymer rubbercontaining a hydrolyzable silyl group, represented by the followinggeneral formula (1):

wherein, R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; Xis a hydrolyzable group selected from the group consisting of hydride,halogen, alkoxyl, acyloxy, ketoximate, amide, acid amide, aminoxy,thioalkoxy, amino, mercapto and alkenyloxy group; and “m” is an integerof 0 to 2, (K3) an epoxy resin, (Q) a silicon compound containing afunctional group reactive with an epoxy group and a hydrolyzable silylgroup in the molecule, and (R) a silicon compound containing at leasttwo hydroxyl groups bonded to the silicon atom in the molecule.
 17. Arubber composition comprising (A2) a silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubbercontaining a hydrolyzable silyl group, represented by the followinggeneral formula (1):

wherein, R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; Xis a hydrolyzable group selected from the group consisting of hydride,halogen, alkoxyl, acyloxy, ketoximate, amide, acid amide, aminoxy,thioalkoxy, amino, mercapto and alkenyloxy group; and “m” is an integerof 0 to 2, wherein the rubber (A2) is produced by hydrosilylation,whereby said ethylene/α-olefin/non-conjugated polyene random copolymerrubber is reacted with a silicon compound represented by the followinggeneral formula (6) in the presence of a transition metal complexcatalyst:

wherein R and “m” are as defined above; (L1) calcium carbonate, and (L2)talc.
 18. The rubber composition according to any one of claims 13 to17, wherein said silyl-containing ethylene/α-olefin/non-conjugatedpolyene random copolymer rubber (A2) has at least one type of silylgroup containing units represented by the following general formula (2)or (3):

wherein, R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; R¹is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; R² is ahydrogen atom or an alkyl group of 1 to 5 carbon atoms; R³ is a hydrogenatom or an alkyl group of 1 to 10 carbon atoms; X is a hydrolyzablegroup selected from the group consisting of hydride, halogen, alkoxyl,acyloxy, ketoximate, amide, acid amide, aminoxy, thioalkoxy, amino,mercapto and alkenyloxy group; and “m” is an integer of 0 to 2 and “n”is an integer of 0 to
 10. 19. The rubber composition according to anyone of claims 13 to 17, wherein said silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A2) isproduced by reacting an ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber having a norbornene compound as the non-conjugatedpolyene with at least one terminal vinyl group represented by thefollowing general formula (4) and/or (5):

wherein, R¹ is a hydrogen atom or an alkyl group of 1 to 10 carbonatoms; R² is a hydrogen atom or an alkyl group of 1 to 5 carbon atoms;R³ is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; and “n”is an integer of 0 to 10, with a silicon compound represented by thefollowing general formula (6):

wherein, R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; Xis a hydrolysable group selected from the group consisting of hydride,halogen, alkoxyl, acyloxy, ketoximate, amide, acid amide, aminoxy,thioalkoxy, amino, mercapto and alkenyloxy group; and “m” is an integerof 0 to 2, to add the SiH group of the silicon compound to the doublebond of the copolymer rubber.
 20. A curable composition comprising (a) asilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1) which has a structural unit derived from anorbornene compound, represented by the following general formula [I] or[II], as the non-conjugated polyene with at least one specific vinylgroup at the terminal, and containing a hydrolyzable silyl group,represented by the following general formula [III], and

wherein, “n” isan integer of 0 to 10; R¹ is a hydrogen atom or an alkylgroup of 1 to 10 carbon atoms; and R² is a hydrogen atom or an alkylgroup of 1 to 5 carbon atoms,

wherein, R³ is a hydrogen atom or an alkyl group of 1 to 10 carbonatoms,

wherein, R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; Xis a hydrolyzable group selected from the group consisting of hydride,halogen, mercapto, alkenyloxy, alkoxyl, acyloxy, ketoximate, amide, acidamide, aminoxy, thioalkoxy and amino group; and “a” is an integer of 0to 2, (b) a nickel-containing light stabilizer (S) and (c) a silanecoupling agent (T).
 21. A curable rubber composition comprising asilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1) which has a structural unit derived from anorbomene compound, represented by the following general formula [I] or[II], as the non-conjugated polyene with at least one specific vinylgroup at the terminal, and containing a hydrolyzable silyl group,represented by the following general formula [III], and

wherein, “n” is an integer of 0 to 10; R¹ is a hydrogen atom or an alkylgroup of 1 to 10 carbon atoms; and R² is a hydrogen atom or an alkylgroup of 1 to 5 carbon atoms,

wherein, R³ is a hydrogen atom or an alkyl group of 1 to 10 carbonatoms,

wherein, R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; Xis a hydrolyzable group selected from the group consisting of hydride,halogen, alkoxyl, acyloxy, ketoximate, amide, acid amide, aminoxy,mercapto, alkenyloxy, thioalkoxy and amino group; and “a” is an integerof 0 to 2, and a sulfur-based aging inhibitor (U).
 22. A curablecomposition comprising (A1) a silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber whichhas a structural unit derived from a norbomene compound, represented bythe following general formula [I] or [II], as the non-conjugated polyenewith at least one specific vinyl group at the terminal, and containing ahydrolyzable silyl group, represented by the following general formula[III], and

wherein, “n” is an integer of 0 to 10; R¹ is a hydrogen atom or an alkylgroup of 1 to 10 carbon atoms; and R² is a hydrogen atom or an alkylgroup of 1 to 5 carbon atoms,

wherein, R³ is a hydrogen atom or an alkyl group of 1 to 10 carbonatoms,

wherein, R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; Xis a hydrolyzable group selected from the group consisting of hydride,halogen, mercapto, alkenyloxy, alkoxyl, acyloxy, ketoximate, amide, acidamide, aminoxy, thioalkoxy and amino group; and “a” is an integer of 0to 2, and (V) a compound having, in the molecule, an unsaturated groupcapable of triggering polymerization by reacting with oxygen in airandlor a photopolymerizable material.
 23. An adhesive compositioncomprising a silyl-containing ethylene/α-olefin/non-conjugated polyenerandom copolymer rubber (A1) which has a structural unit derived from anorbomene compound, represented by the following general formula [I] or[II], as the non-conjugated polyene with at least one specific vinylgroup at the terminal, and containing a hydrolyzable silyl group,represented by the following general formula [III], and

wherein, “n” is an integer of 0 to 10; R¹ is a hydrogen atom or an alkylgroup of 1 to 10 carbon atoms; and R² is a hydrogen atom or an alkylgroup of 1 to 5 carbon atoms,

wherein, R³ is a hydrogen atom or an alkyl group of 1 to 10 carbonatoms,

wherein, R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; Xis a hydrolyzable group selected from the group consisting of hydride,halogen, alkoxyl, acyloxy, ketoximate, amide, acid amide, aminoxy,mercapto, alkenyloxy, thioalkoxy and amino group; and “a” is an integerof 0 to 2, a tackiness imparting resin (W), and a curing catalyst (H)composed of an organozirconium compound (H1) represented by thefollowing general formula [VIII] or an organoaluminum compound (H2)represented by the following general formula [IX]:

wherein, “n” is an integer of 0 to 4, R is a monovalent hydrocarbongroup of 1 to 20 carbon atoms, and Y is a group selected from the groupconsisting of hydrocarbon of 1 to 8 carbon atoms, halogenatedhydrocarbon, cyanoalkyl, alkoxyl, halogenated alkoxyl, cyanoalkoxy andamino group, which may be the same or different, and

wherein, “p” is an integer of 0 to 3, R is a monovalent hydrocarbongroup of 1 to 20 carbon atoms, and Y is a group selected from the groupconsisting of hydrocarbon of 1 to 8 carbon atoms, halogenatedhydrocarbon, cyanoalkyl, alkoxyl, halogenated alkoxyl, cyanoalkoxy andamino group, which may be the same or different.
 24. A rubbercomposition of improved pot life, comprising a silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A1)which has a structural unit derived from a norbornene compound,represented by the following general formula [I] or [II], as thenon-conjugated polyene with at least one specific vinyl group at theterminal, and containing a hydrolyzable silyl group, represented by thefollowing general formula [III], and

wherein, “n” is an integer of 0 to 10; R¹ is a hydrogen atom or an alkylgroup of 1 to 10 carbon atoms; and R² is a hydrogen atom or an alkylgroup of 1 to 5 carbon atoms,

wherein, R³ is a hydrogen atom or an alkyl group of 1 to 10 carbonatoms,

wherein, R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; Xis a hydrolyzable group selected from the group consisting of hydride,halogen, alkoxyl, acyloxy, ketoximate, amide, acid amide, aminoxy,mercapto, alkenyloxy, thioalkoxy and amino group; and “a” is an integerof 0 to 2, a curing catalyst (H) composed of a mercaptide type organotincompound (H3) having the Sn—S bond, a sulfide type organotin compound(H4) having the Sn═S bond, organocarboxylic acid (H5), organocarboxylicanhydride (H6), or a mixture of one of the above compounds and acarboxylic type organotin compound (H7).
 25. A curable compositioncomprising (A1) a silyl-containing ethylene/α-olefin/non-conjugatedpolyene random copolymer rubber which has a structural unit derived froma norbornene compound, represented by the following general formula [I]or [II], as the non-conjugated polyene with at least one specific vinylgroup at the terminal, and containing a hydrolyzable silyl group,represented by the following general formula [III], and

wherein, “n” is an integer of 0 to 10; R¹ is a hydrogen atom or an alkylgroup of 1 to 10 carbon atoms; and R² is a hydrogen atom or an alkylgroup of 1 to 5 carbon atoms,

wherein, R³ is a hydrogen atom or an alkyl group of 1 to 10 carbonatoms,

wherein, R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; Xis a hydrolyzable group selected from the group consisting of hydride,halogen, mercapto, alkenyloxy, alkoxyl, acyloxy, ketoximate, amide, acidamide, aminoxy, thioalkoxy and amino group; and “a” is an integer of 0to 2, wherein the rubber (A1) is produced by hydrosilylation, wherebysaid ethylene/α-olefin/non-conjugated polyene random copolymer rubber isreacted with a silicon compound represented by the following generalformula [IV] in the presence of a transition metal complex catalyst:

wherein R and “a” are as defined above; and (H8) a compound as a curingcatalyst (H), represented by the general formula Q₂Sn(OZ)₂ or[Q₂Sn(OZ)]₂O, wherein, Q is a monovalent hydrocarbon group of 1 to 20carbon atoms; and Z is a monovalent hydrocarbon group of 1 to 20 carbonatoms or an organic group having a functional group capable of formingtherein a coordination bond with Sn.
 26. A curable rubber compositioncomprising a silyl-containing ethylene/α-olefin/non-conjugated polyenerandom copolymer rubber (A1) which has a structural unit derived from anorbomene compound, represented by the following general formula [I] or[II], as the non-conjugated polyene with at least one specific vinylgroup at the terminal, and containing a hydrolyzable silyl group,represented by the following general formula [III], and

wherein, “n” is an integer of 0 to 10; R¹ is a hydrogen atom or an alkylgroup of 1 to 10 carbon atoms; and R² is a hydrogen atom or an alkylgroup of 1 to 5 carbon atoms,

wherein, R³ is a hydrogen atom or an alkyl group of 1 to 10 carbonatoms,

wherein, R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; Xis a hydrolyzable group selected from the group consisting of hydride,halogen, alkoxyl, acyloxy, ketoximate, amide, acid amide, aminoxy,mercapto, alkenyloxy, thioalkoxy and amino group; and “a” is an integerof 0 to 2, wherein the rubber (A1) is produced by hydrosilylation,whereby said ethylene/α-olefin/non-conjugated polyene random copolymerrubber is reacted with a silicon compound represented by the followinggeneral formula [IV] in the presence of a transition metal complexcatalyst:

wherein R and “a” are as defined above; and titanates (Y).
 27. A sealantfor laminated glass, comprising (A2) a silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubbercontaining a hydrolyzable silyl group, represented by the followinggeneral formula (1):

wherein, R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; Xis a hydrolyzable group selected from the group consisting of hydride,halogen, alkoxyl, acyloxy, ketoximate, amide, acid amide, aminoxy,thioalkoxy, amino, mercapto and alkenyloxy group; and “m” is an integerof 0 to 2, wherein the rubber (A2) is produced by hydrosilylation,whereby said ethylene/α-olefin/non-conjugated polyene random copolymerrubber is reacted with a silicon compound represented by the followinggeneral formula (6) in the presence of a transition metal complexcatalyst:

wherein R and “m” are as defined above; (H) a curing catalyst, and (B11)water or a hydrate of a metallic salt.
 28. A sealant for laminatedglass, comprising (A2) a silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubbercontaining a hydrolyzable silyl group, represented by the followinggeneral formula (1):

wherein, R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; Xis a hydrolyzable group selected from the group consisting of hydride,halogen, alkoxyl, acyloxy, ketoximate, amide, acid amide, aminoxy,thioalkoxy, amino, mercapto and alkenyloxy group; and “m” is an integerof 0 to 2, (X) a hot melt resin, (H) a curing catalyst, and (B11) wateror a hydrate of a metallic salt.
 29. The sealant for laminated glassaccording to claim 27 or 28, wherein said silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A2)has at least one type of silyl-containing units represented by thegeneral formula (2) or (3):

wherein, R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; R¹is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; R² is ahydrogen atom or an alkyl group of 1 to 5 carbon atoms; R³ is a hydrogenatom or an alkyl group of 1 to 10 carbon atoms; X is a hydrolyzablegroup selected from the group consisting of hydride, halogen, alkoxyl,acyloxy, ketoximate, amide, acid amide, aminoxy, thioalkoxy, amino,mercapto and alkenyloxy group; and “m” is an integer of 0 to 2 and “n”is an integer of 0 to
 10. 30. The sealant for laminated glass accordingto one of claim 27 to 28, wherein said silyl-containingethylene/α-olefin/non-conjugated polyene random copolymer rubber (A2) isproduced by reacting an ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber having a norbornene compound as the non-conjugatedpolyene with at least one terminal vinyl group represented by thefollowing general formula (4) and/or (5):

wherein, R¹ is a hydrogen atom or an alkyl group of 1 to 10 carbonatoms; R² is a hydrogen atom or an alkyl group of 1 to 5 carbon atoms;R³ is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; and “n”is an integer of 0 to 10, with a silicon compound represented by thefollowing general formula (6):

wherein, R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; Xis a hydrolysable group selected from the group consisting of hydride,halogen, alkoxyl, acyloxy, ketoximate, amide, acid amide, aminoxy,thioalkoxy, amino, mercapto and alkenyloxy group; and “m” is an integerof 0 to 2, to add the SiH group of the silicon compound to the doublebond of the copolymer rubber.
 31. The rubber composition according toclaim 18, wherein said silyl-containing ethylene/α-olefin/non-conjugatedpolyene random copolymer rubber (A2) is produced by reacting anethylene/α-olefin/non-conjugated polyene random copolymer rubber havinga norbomene compound as the non-conjugated polyene with at least oneterminal vinyl group represented by the following general formula (4)and/or (5):

wherein, R¹ is a hydrogen atom or an alkyl group of 1 to 10 carbonatoms; R² is a hydrogen atom or an alkyl group of 1 to 5 carbon atoms;R³ is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; and “n”is an integer of 0 to 10, with a silicon compound represented by thefollowing general formula (6):

wherein, R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; Xis a hydrolysable group selected from the group consisting of hydride,halogen, alkoxyl, acyloxy, ketoximate, amide, acid amide, aminoxy,thioalkoxy, amino, mercapto and alkenyloxy group; and “m” is an integerof 0 to 2, to add the SiH group of the silicon compound to the doublebond of the copolymer rubber.
 32. The rubber composition according toclaim 29, wherein said silyl-containing ethylene/α-olefin/non-conjugatedpolyene random copolymer rubber (A2) is produced by reacting anethylene/α-olefin/non-conjugated polyene random copolymer rubber havinga norbornene compound as the non-conjugated polyene with at least oneterminal vinyl group represented by the following general formula (4)andlor (5):

wherein, R¹ is a hydrogen atom or an alkyl group of 1 to 10 carbonatoms; R² is a hydrogen atom or an alkyl group of 1 to 5 carbon atoms;R³ is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; and “n”is an integer of 0 to 10, with a silicon compound represented by thefollowing general formula (6):

wherein , R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; Xis a hydrolyzable group selected from the group consisting of hydride,halogen, alkoxyl, acyloxy, ketoximate, amide, acid amide, aminoxy,thioalkoxy, amino, mercapto and alkenyloxy group; and “m” is an integerof 0 to 2, to add the SiH group of the silicon compound to the doublebond of the copolymer rubber.
 33. A curable composition comprising asilyl-containing ethylene/α-olefin/non-conjugated polyene randomcopolymer rubber (A1) which has a structural unit derived from anorbomene compound, represented by the following general formula [I] or[II], as the non-conjugated polyene with at least one specific vinylgroup at the terminal, and containing a hydrolyzable silyl group,represented by the following general formula [III], and

wherein, “n” isan integer of 0 to 10; R¹ is a hydrogen atom or an alkylgroup of 1 to 10 carbon atoms; and R² is a hydrogen atom or an alkylgroup of 1 to 5 carbon atoms,

wherein, R³ is a hydrogen atom or an alkyl group of 1 to 10 carbonatoms,

wherein, R is a monovalent hydrocarbon group of 1 to 12 carbon atoms; Xis a hydrolyzable group selected from the group consisting of hydride,halogen, alkoxyl, acyloxy, ketoximate, amide, acid amide, aminoxy,mercapto, alkenyloxy, thioalkoxy and amino group; and “a” is an integerof 0 to 2, wherein the rubber (A1) is produced by hydrosilylation,whereby said ethylene/α-olefin/non-conjugated polyene random copolymerrubber is reacted with a silicon compound represented by the followinggeneral formula [IV] in the presence of a transition metal complexcatalyst:

wherein R and “a” are as defined above; and a compound (B), other thanthe rubber (A1), containing silicon and having a hydroxyl group andlor ahydrolyzable group.
 34. An electric/electronic device member,transportation machine, civil engineering/construction, medical productor leisure product prepared from the composition of claims 1–17 or20–26.
 35. An electric/electronic device member, transportation machine,civil engineering/construction, medical product or leisure productprepared from the composition of claim
 18. 36. An electric/electronicdevice member, transportation machine, civil engineering/construction,medical product or leisure product prepared from the composition ofclaim
 19. 37. A sealant, potting material, coating material or adhesivefor electrical/electronic devices, transportation machines, civilengineering/construction materials, medical products and leisureproducts prepared from the compositions of claims 1–17 or 20–26.
 38. Asealant, potting material, coating material or adhesive forelectrical/electronic devices, transportation machines, civilengineering/construction materials, medical products or leisure productsprepared from the composition of claim
 18. 39. A sealant, pottingmaterial, coating material or adhesive for electrical/electronicdevices, transportation machines, civil engineering/constructionmaterials, medical products or leisure products prepared from thecomposition of claim
 19. 40. The curable rubber composition according toclaim 10, wherein the hydrolysable organosilicon compound (B10) is atleast one compound selected from the group consisting oftrimethoxysilane, triethoxysilane, methyldiethoxysilane,methyldimethoxysilane, phenyldimethoxysilane, ethyldiethoxysilane,ethyldimethoxysilane, butyldiethoxysilane, butyldimethoxysilane,methyltrimethoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane,phenyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane,butyltriethoxysilane, phenyltriethoxysilane, dimethyldiethoxysilane,dibutyldiethoxysilane, and diphenyldiethoxysilane.